Propylene polymer, propylene copolymer, and propylene elastomer prepared using novel bridged indenyl containing metallocenes

ABSTRACT

The novel transition metal compound of the invention is represented by the following formula (I): ##STR1## wherein M is a transition metal; R 1  and R 2  are each a hydrogen atom, a hydrocarbon group or the like; R 3  is an alkyl group of 2 to 20 carbon atoms; R 4  is an alkyl group of 2 to 20 carbon atoms; X 1  and X 2  are each a halogen atom or the like; and Y is a divalent hydrocarbon group, a divalent silicon-containing group or the like. 
     The transition metal compound is useful for an olefin polymerization catalyst with which a propylene (co)polymer having specific structure is prepared.

FIELD OF THE INVENTION

The present invention relates to a novel transition metal compound, anolefin polymerization catalyst component comprising the transition metalcompound, an olefin polymerization catalyst containing the catalystcomponent and a process for olefin polymerization using the olefinpolymerization catalyst. The invention also relates to a propylenepolymer, a propylene copolymer and a propylene elastomer, all having ahigh triad tacticity of the propylene unit chain.

BACKGROUND OF THE INVENTION

A well known homogeneous catalyst is, for example, so-called Kaminskycatalyst. Use of this Kaminsky catalyst produces a polymer having anextremely high polymerization activity and a narrow molecular weightdistribution.

Of the Kaminsky catalysts, ethylenebis(indenyl)zirconium dichloride andethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride are known astransition metal compounds for preparing isotactic polyolefins, asdescribed in Japanese Patent Laid-Open Publication No. 130314/1986.However, polyolefins prepared by the use of these catalysts generallyhave a low stereoregularity and a low molecular weight. As a process forpreparing polyolefins of high stereoregularity and high molecular weightusing these catalyst, there is a process in which the polymerization isconducted at a low temperature, but this process has a problem of lowpolymerization activity.

It is known that use of hafnium compounds in place of the zirconiumcompounds makes it possible to prepare a polymer having high molecularweight, as described in "Journal of Molecular Catalysis", 56 (1989), pp.237-247, but this process also has a problem of low polymerizationactivity. Further, dimethylsilyl bissubstituted cyclopentadienylzirconium dichloride is also known as described in Japanese PatentLaid-Open Publication No. 301704/1989 and "Polymer Preprints", Japan,vol. 39, No. 6, pp. 1,614-1,616 (1990), but this compound is notsatisfactory in all of polymerization activity, and stereoregularity andmolecular weight of polymers obtained.

In order to solve these problems, various proposals have been made. Forexample, Japanese Patent Laid-Open Publication 268307/1993 describes anolefin polymerization catalyst formed from a metallocene compoundrepresented by the following formula and aluminoxane as a catalystcapable of preparing a high molecular polyolefin, but the molecularweight of the resultant polyolefin is still insufficient. ##STR2##

Further, EP 0 530 648 A1 describes an olefin polymerization catalystformed from a metallocene compound represented by the following formulaand aluminoxane. ##STR3## wherein A is a lower alkyl group.

The molecular weight of the polyolefin obtained by the use of thiscatalyst is high and industrially satisfactory. In addition, since themelting point of the polyolefin (e.g., polypropylene) having highstereoregularity becomes high, the catalyst is suitably used forpreparing a stereoregular polyolefin having a high melting point.However, it is unsuitable for preparing a stereoregular polyolefin(particularly a copolymer) having a high molecular weight and a lowmelting point, and the resultant polyolefin or copolymer is notsatisfactory in its quality.

Furthermore, EP 0 537 686 describes an olefin polymerization catalystformed from a metallocene compound represented by the following formulaand aluminoxane. ##STR4## wherein R¹ and R² are each a methyl group orhydrogen, X is Si(CH₃)₂ group or an ethylene group.

However, a polyolefin obtained by the use of this catalyst is low in themolecular weight and cannot be practically used.

Under such circumstances as mentioned above, an olefin polymerizationcatalyst and a process for olefin polymerization, both having higholefin polymerization activity and being capable of preparing apolyolefin of excellent properties, are desired. Further, also desiredare an olefin polymerization catalyst component used for such catalystand a novel transition metal compound capable of forming the olefinpolymerization catalyst component. In the light of the existingcircumstances, the present inventors have earnestly studied, and as aresult, they have found that the above requirements are satisfied by atransition metal compound which has two indenyl groups having a specificsubstituent group, said two indenyl groups being linked by way of ahydrocarbon group, a silicon-containing group or the like.

Propylene polymers have been applied to various uses because of theirexcellent mechanical properties and optical properties. For example, apropylene homopolymer is excellent in rigidity, surface hardness, heatresistance, glossiness and transparency, and hence it is used forvarious industrial parts, containers, films and nonwoven fabrics. Apropylene/ethylene random copolymer containing a small amount ofethylene units is excellent in transparency, ridigity, surface hardness,heat resistance, heat-sealing properties, and hence it is used forfilms, containers, etc. A propylene elastomer is excellent in impactabsorbing properties, heat resistance and heat-sealing properties, andhence it is singly used for films or used as a modifier of athermoplastic resin.

However, the conventional propylene polymer is not always sufficient intransparency, impact resistance, etc. for some uses, and therefore theadvent of a propylene polymer excellent in rigidity, heat resistance,surface hardness, glossiness, transparency and impact strength isdesired. The conventional propylene/ethylene random copolymer is notalways sufficient in transparency, heat-sealing properties,anti-blocking properties, bleed resistance, impact strength, etc. forsome uses, and therefore the advent of a propylene/ethylene randomcopolymer excellent in transparency, rigidity, surface harness, heatresistance and heat-sealing properties is desired. The conventionalpropylene elastomer is not always sufficient in heat-sealing properties,anti-blocking properties and heat resistance when used singly, and isnot always sufficient in effect of improving impact resistance when usedas a modifier. Therefore, a propylene elastomer excellent in impactresistance, heat resistance, transparency, heat-sealing properties,anti-blocking properties and effect of improving impact resistance isdesired.

In the light of such circumstances as described above, the presentinventors have further studied, and as a result, they have found that apropylene homopolymer having a high triad tacticity, as measured by ¹³C-NMR, of the propylene chain consisting of head-to-tail bonds, aspecific proportion of inversely inserted propylene units and a specificintrinsic viscosity is excellent in the above-mentioned properties.Further, they have also found that a propylene copolymer which containsa small amount of ethylene units and has a high triad tacticity, asmeasured by ¹³ C-NMR, of the propylene chain consisting of head-to-tailbonds, a specific proportion of inversely inserted propylene units and aspecific intrinsic viscosity is excellent in the above-mentionedproperties. Furthermore, they have found that a propylene elastomerwhich contains a specific amount of ethylene units and has a high triadtacticity, as measured by ¹³ C-NMR, of the propylene chain consisting ofhead-to-tail bonds, a specific proportion of inversely insertedpropylene units and a specific intrinsic viscosity is excellent in theabove-mentioned properties.

Moreover, the present inventors have found that the propylene polymer,the propylene copolymer and the propylene elastomer can be prepared bythe use of an olefin polymerization catalyst containing the aforesaidspecific transition metal compound as a catalyst component.

OBJECT OF THE INVENTION

It is an object of the present invention to provide a novel transitionmetal compound useful for an olefin polymerization catalyst componenthaving a high olefin polymerization activity and to provide an olefinpolymerization catalyst component comprising said transition metalcompound.

It is another object of the invention to provide an olefinpolymerization catalyst containing the above olefin polymerizationcatalyst component and to provide a process for olefin polymerizationusing said olefin polymerization catalyst.

It is a further object of the invention to provide a propylene polymerhaving excellent properties.

SUMMARY OF THE INVENTION

The novel transition metal compound according to the invention is atransition metal compound represented by the following formula (I):##STR5## wherein M is a transition metal of Group IVa, Group Va andGroup VIa of the periodic table;

R¹ and R² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, a silicon-containing group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group or aphosphorus-containing group;

R³ is an alkyl group of 2 to 20 carbon atoms;

R⁴ is an alkyl group of 1 to 20 carbon atoms;

X¹ and X² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, an oxygen-containing group or a sulfur-containing group;and

Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, adivalent tin-containing group, --O--, --CO--, --S--, --SO--, --SO₂ --,--NR⁵ --, --P(R⁵)--, --P(O)(R⁵)--, --BR⁵ -- or --A1R⁵ -- (R⁵ is ahydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms) .

The olefin polymerization catalyst component according to the inventioncomprises a transition metal compound represented by the above formula(I).

The first olefin polymerization catalyst according to the inventioncomprises:

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The second olefin polymerization catalyst according to the inventioncomprises:

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

(C) an organoaluminum compound.

The third olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair;

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier.

The fourth olefin polymerization catalyst according to the inventioncomprises:

a solid catalyst component comprising:

a fine particle carrier,

(A) a transition metal compound represented by the above formula (I),and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair,

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier; and

(C) an organoaluminum compound.

The fifth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

a prepolymerized olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair;

(C) an organoaluminum compound; and

a prepolymerized olefin polymer produced by prepolymerization.

The process for olefin polymerization according to the inventioncomprises polymerizing or copolymerizing an olefin in the presence ofany of the first to sixth olefin polymerization catalysts.

The olefin polymerization catalysts according to the invention have highpolymerization activity and an olefin polymer obtained by using thecatalytsts has a narrow molecular weight distribution and a narrowcomposition distribution. When they are used for polymerizing anα-olefin of 3 or more carbon atoms, obtainable is a polymer having alower melting point as compared with a polymer obtained by using aconventional metallocene catalyst when these polymers have similarmolecular weights. Further, in the preparation of a copolymer elastomercontaining ethylene or propylene as its major component, a polymer ofhigh molecular weight can be obtained.

When such catalysts are used, a copolymer having a low melting point canbe obtained even though an amount of comonomer units is small.

The propylene polymer according to the invention has such propertiesthat:

(a) a triad tacticity of three propylene units-chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 90.0%;

(b) a proportion of the inversely inserted propylene units based on the2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, is not less than 0.7%, and the proportion of theinversely inserted propylene units based on the 1,3-insertion of apropylene monomer, as measured by ¹³ C-NMR, is not more than 0.05%; and

(c) the intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 12 dl/g.

Such propylene polymer is excellent in rigidity, heat resistance,surface hardness, glossiness, transparency and impact resistance.

The propylene copolymer according to the invention has such propertiesthat:

(a) said copolymer contains propylene units in an amount of 95 to 99.5%by mol and ethylene units in an amount of 0.5 to 5% by mol;

(b) a triad tacticity of three propylene units-chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 90.0%;

(c) a proportion of inversely inserted propylene units based on the2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, is not less than 0.5%, and a proportion ofinversely inserted propylene units based on the 1,3-insertion of apropylene monomer, as measured by ¹³ C-NMR, is not more than 0.05%; and

(d) the intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 12 dl/g.

Such propylene copolymer is excellent in transparency, rigidity, surfacehardness, heat resistance, heat-sealing properties, bleed resistance andimpact resistance.

The propylene elastomer according to the invention has such propertiesthat:

(a) said elastomer contains propylene units in an amount of 50 to 95% bymol and ethylene units in an amount of 5 to 50% by mol;

(b) a triad tacticity of three propylene units-chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is not less than 90.0%;

(c) a proportion of inversely inserted propylene units based on the2,1-insertion of a propylene monomer in all propylene insertions, asmeasured by ¹³ C-NMR, is not less than 0.5%, and a proportion ofinversely inserted propylene units based on the 1,3-insertion of apropylene monomer, as measured by ¹³ C-NMR, is not more than 0.05%; and

(d) the intrinsic viscosity, as measured in decahydronaphthalene at 135°C., is in the range of 0.1 to 12 dl/g.

Such propylene elastomer is excellent in heat resistance, impactabsorbing properties, transparency, heat-sealing properties andanti-blocking properties.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a view illustrating steps of a process for preparing the firstand the second olefin polymerization catalysts according to theinvention.

FIG. 2 is a view illustrating steps of a process for preparing the thirdand the fourth olefin polymerization catalysts according to theinvention.

FIG. 3 is a view illustrating steps of a process for preparing the fifthand the sixth olefin polymerization catalysts according to theinvention.

DETAILED DESCRIPTION OF THE INVENTION

The novel transition metal compound, the olefin polymerization catalystcomponent comprising the transition metal compound, the olefinpolymerization catalyst containing the olefin polymerization catalystcomponent, the process for olefin polymerization using the olefinpolymerization catalyst, the propylene polymer, the propylene copolymerand the propylene elastomer, according to the invention, will bedescribed in detail hereinafter.

FIG. 1 is a view illustrating steps of a process for preparing the firstand the second olefin polymerization catalysts according to theinvention. FIG. 2 is a view illustrating steps of a process forpreparing the third and the fourth olefin polymerization catalystsaccording to the invention. FIG. 3 is a view illustrating steps of aprocess for preparing the fifth and the sixth olefin polymerizationcatalysts according to the invention.

First, the novel transition metal compound according to the invention isdescribed.

The novel transition metal compound of the invention is a transitionmetal compound represented by the following formula (I). ##STR6##

In the formula (I), M is a transition metal of Group IVa, Group Va andGroup VIa of the periodic table. Examples of the transition metalsinclude titanium, zirconium, hafnium, vanadium, niobium, tantalum,chromium, molybdenum and tungsten. Of these, titanium, zirconium andhafnium are preferred, and zirconium is particularly preferred.

R¹ and R² are each independently a hydrogen atom, a halogen atom, ahydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbongroup of 1 to 20 carbon atoms, a silicon-containing group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group or a phosphorus-containing group.

Examples of the halogen atoms include fluorine, chlorine, bromine andiodine.

Examples of the hydrocarbon groups of 1 to 20 carbon atoms include analkyl group such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl,octyl, nonyl, dodecyl, icosyl, norbornyl and adamantyl; an alkenyl groupsuch as vinyl, propenyl and cyclohexenyl; arylalkyl group such asbenzyl, phenylethyl and phenylpropyl; and an aryl group such as phenyl,tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl,biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl.

Examples of the halogenated hydrocarbon groups include halogenatedhydrocarbon groups of the above-mentioned hydrocarbon groups.

Examples of the silicon-containing groups includemonohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl;dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;trihydrocarbon-substituted silyl such as trimethylsilyl, triethylsilyl,tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl,methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyloxy ofhydrocarbon-substituted silyl such as trimethylsilyloxy;silicon-substituted alkyl group particularly trilower alkylsilylmethylgroup such as trimethylsilylmethyl; and silicon-substituted aryl groupparticularly trilower alkylsilylphenyl group such as trimethylphenyl. Inthis regard, the hydrocarbon is preferably lower alkyl, cyclohexyl,phenyl, tolyl or naphthyl.

Examples of the oxygen-containing groups include a hydroxy group; analkoxy group particularly lower alkoxy group such as methoxy, ethoxy,propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy,dimethylphenoxy and naphthoxy; and an arylalkoxy group such as benzyloxyand phenylethoxy.

Examples of the sulfur-containing groups include groups obtained bysubstituting sulfur for oxygen in the above-mentioned oxygen-containinggroups, such as mercapto; lower alkythio group; arylthio group; andarylalkylthio.

Examples of the nitrogen-containing groups include an amino group; analkylamino group such as methylamino, dimethylamino, diethylamino,dipropylamino, dibutylamino and dicyclohexylamino; an arylamino groupsuch as phenylamino, diphenylamino, ditolylamino, dinaphthylamino andmethylphenylamino; and an alkylarylamino group.

Examples of the phosphorus-containing groups include a phosphino groupsuch as dimethylphosphino and diphenylphosphino.

Of these, R¹ is preferably a hydrocarbon group, particularly an alkylgroup of 1 to 3 carbon atoms such as methyl, ethyl and propyl. R² ispreferably a hydrogen atom or a hydrocarbon group, particularly ahydrogen atom or an alkyl group of 1 to 3 carbon atoms such as methyl,ethyl and propyl.

R³ is an alkyl group of 2 to 20 carbon atoms or an arylalkyl group of upto 20 carbon atoms, and R⁴ is an alkyl group of 1 to 20 carbon atoms oran arylalkyl group of up to 20 carbon atoms. R³ is preferably asecondary or tertiary alkyl group. The alkyl group indicated by R³ or R⁴may be substituted with a halogen atom or a silicon-containing group.Examples of the halogen atoms and examples or the silicon-containinggroups are those exemplified above with respect to R¹ and R².

Examples of the alkyl groups indicated by R³ include:

a chain alkyl group and a cyclic alkyl group, such as ethyl, n-propyl,i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl,cyclohexyl, heptyl, octyl, nonyl, dodecyl, icosyl, norbornyl andadamantyl; and

an arylalkyl group, such as benzyl, phenylethyl, phenylpropyl andtolylmethyl.

These groups may be substituted with groups containing a double bond ora triple bond.

Examples of the alkyl groups indicated by R⁴ include methyl, and thechain alkyl groups, the cyclic alkyl groups and the arylalkyl groupsexemplified above with respect to R³.

X¹ and X² are each a hydrogen atom, a halogen atom, a hydrocarbon groupof 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20carbon atoms, an oxygen-containing group or a sulfur-containing group.Examples of those atoms and groups include the halogen atoms, thehydrocarbon groups of 1 to 20 carbon atoms, the halogenated hydrocarbongroups of 1 to 20 carbon atoms and the oxygen-containing groupsexemplified above with respect to R¹ and R².

As the sulfur-containing group, there can be mentioned a sulfonato groupsuch as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato,benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; and a sulfinato group such asmethylsulfinato, phenylsulfinato, benzenesulfinato, p-toluenesulfinato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato.

Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group of 1 to 20 carbon atoms, a divalentsilicon-containing group, a divalent germanium-containing group, adivalent tin-containing group, --O--, --CO--, --S--, --SO--, --SO₂ --,--NR⁵ --, --P(R⁵)--, --P(O)(R⁵)--, --BR⁵ -- or --A1R⁵ -- (R⁵ is ahydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms).

Examples of the divalent hydrocarbon groups of 1 to 20 carbon atomsinclude an alkylene group such as methylene, dimethylmethylene,1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene,1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; and anarylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene.

Examples of the halogenated hydrocarbon groups include groups obtainedby halogenating the above-mentioned hydrocarbon groups of 1 to 20 carbonatoms, such as chloromethylene.

Examples of the silicon-containing groups include an alkylsilylenegroup, an alkylarylsilylene group and an arylsilylene group, such asmethylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene,di(i-propyl)silylene, di(cyclohexyl)silylene, methylphenylsilylene,diphenylsilylene, di(p-tolyl)silylene and di(p-chlorophenyl)silylene;and an alkyldisilyl group, an alkylaryldisilyl group and an arylsilylgroup, such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl. Thealkylsilylene group may be a mono-alkylsilylene group or adialkylsilylene group. The alkyl is preferably a lower alkyl of 1 to 4carbon atoms or cycloalkyl. The arylsilylene group may be amono-arylsilylene or a diarylsilylene and the aryl is preferably phenylwhich may be substituted by a lower alkyl or halogen.

Examples of the divalent germanium-containing groups include groupsobtained by substituting germanium for silicon in the above-mentioneddivalent silicon-containing groups.

Examples of the divalent tin-containing groups include groups obtainedby substituting tin for silicon in the above-mentioned divalentsilicon-containing groups.

Examples of the atoms and the groups indicated by R⁵ include thehydrogen atoms, the halogen atoms, the hydrocarbon groups of 1 to 20carbon atoms and the halogenated hydrocarbon groups of 1 to 20 carbonatoms exemplified above with respect to R¹ and R².

Of these, preferred are a divalent silicon-containing group, a divalentgermanium-containing group and a divalent tin-containing group. Morepreferred is a silicon-containing group. Of the silicon-containinggroups, alkylsilylene, alkylarylsilylene and arylsilylene areparticularly preferred.

Listed below are examples of the transition metal compounds representedby the above formula (I).

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-ethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-n-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-n-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-sec-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-n-pentylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-n-hexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-cyclohexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-methylcyclohexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-phenylethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-phenyldichloromethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-chloromethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-trimethylsilylmethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,7-dimethyl-4-trimethylsiloxymethylindenyl)}zirconiumdichloride,

rac-Diethylsilyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(i-propyl)silyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(n-butyl)silyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(cyclohexyl)silyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Methylphenylsilyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Methylphenylsilyl-bis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,7-dimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,7-dimethyl-4-ethylindenyl)}zirconiumdichloride,

rac-Di(p-tolyl)silyl-bis{1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(p-chlorophenyl)silyl-bis(1-(2,7-dimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-ethylindenyl)}zirconiumdibromide,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-ethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-n-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-n-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-sec-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-n-pentylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-n-hexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-cyclohexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-methylcyclohexylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-trimethylsilylmethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-phenylethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-phenyldichloromethylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2,3,7-trimethyl-4-chloromethylindenyl)}zirconiumdichloride,

rac-Diethylsilyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(i-propyl)silyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(n-butyl)silyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(cyclohexyl)silyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Methylphenylsilyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Methylphenylsilyl-bis{1-(2,3,7-trimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,3,7-trimethyl-4-t-butylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Diphenylsilyl-bis{1-(2,3,7-trimethyl-4-ethylindenyl)}zirconiumdichloride,

rac-Di(p-tolyl)silyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Di(p-chlorophenyl)silyl-bis{1-(2,3,7-trimethyl-4-i-propylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}zirconiumdimethyl,

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}zirconiummethylchloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}zirconium-bis(methanesulfonate),

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}zirconium-bis(p-phenylsulfonate),

rac-Dimethylsilyl-bis{1-(2-methyl-3-methyl-4-i-propyl-7-methylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-ethyl-4-i-propyl-7-methylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-phenyl-4-i-propyl-7-methylindenyl)}zirconiumdichloride,

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}titaniumdichloride, and

rac-Dimethylsilyl-bis{1-(2-methyl-4-i-propyl-7-methylindenyl)}hafniumdichloride.

Of these, compounds having a branched alkyl group (e.g., i-propyl,sec-butyl and tert-butyl) at the fourth position are particularlypreferred.

In the present invention, also employable are transition metal compoundswherein the zirconium metal is substituted for titanium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten in theabove-listed compounds.

The indene derivative ligand of the novel transition metal compoundaccording to the invention can be synthesized by an organic synthesismethod conventionally used through the following reaction route.##STR7##

The transition metal compound of the invention can be synthesized fromthe indene derivative by conventionally known methods, for example, amethod described in Japanese Patent Laid-Open Publication No.268307/1993.

The novel transition metal compound according to the invention can beused as an olefin polymerization catalyst component in combination withan organoaluminum oxy-compound, etc.

The transition metal compound is used as an olefin polymerizationcatalyst component in the form of usually a racemic modification, butthe R configuration or the S configuration can be also used.

Next, the olefin polymerization catalyst containing the above-mentionednovel transition metal compound as its catalyst component is described.

The meaning of the term "polymerization" used herein is not limited to"homopolymerization" but may comprehend "copolymerization". Also, themeaning of the term "polymer" used herein is not limited to"homopolymer" but may comprehend "copolymer".

The first and the second olefin polymerization catalysts according tothe invention are described below.

The first olefin polymerization catalyst of the invention is formedfrom:

(A) a transition metal compound represented by the above formula (I)(sometimes referred to as "component (A)" hereinafter); and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair.

The second olefin polymerization catalyst of the invention is formedfrom:

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) a compound which reacts with the transition metal compound to forman ion pair; and

(C) an organoaluminum compound.

The organoaluminum oxy-compound (B-1) (hereinafter sometimes referred toas "component (B-1)") used for the first and the second olefinpolymerization catalysts of the invention may be a conventionally knownaluminoxane or may be a benzene-insoluble organoaluminum oxy-compound asdescribed in Japanese Patent Laid-Open Publication No. 78687/1990.

The conventionally known aluminoxane can be prepared, for example, bythe following processes.

(1) A process comprising allowing an organoaluminum compound such astrialkylaluminum to react with a suspension of a compound havingadsorbed water or a salt containing water of crystallization, forexample, hydrate of magnesium chloride, copper sulfate, aluminumsulfate, nickel sulfate or cerous chloride in a hydrocarbon solvent.

(2) A process comprising allowing water, ice or water vapor to directlyreact with an organoaluminum compound such as trialkylaluminum in asolvent such as benzene, toluene, ethyl ether and tetrahydrofuran.

(3) A process comprising allowing an organotin oxide such as dimethyltinoxide and dibutyltin oxide to react with an organoaluminum compound suchas trialkylaluminum in a solvent such as decane, benzene and toluene.

The aluminoxane may contain a small amount of an organometalliccomponent. Moreover, the solvent or the unreacted organoaluminumcompound may be distilled off from the recovered solution of aluminoxanedescribed above, and the resultant product may be dissolved again in asolvent.

Examples of the organoaluminum compounds used for preparing aluminoxaneinclude:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,tripentylaluminum, trihexylaluminum, trioctylaluminum andtridecylaluminum;

tricycloalkylaluminums, such as tricyclohexylaluminum andtricyclooctylaluminum;

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminumchloride;

dialkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride;

dialkylaluminum alkoxides, such as dimethylaluminum methoxide anddiethylaluminum ethoxide; and

dialkylaluminum aryloxides, such as diethylaluminum phenoxide.

Of the organoaluminum compounds, trialkylaluminum andtricycloalkylaluminum are particularly preferred.

Further, there may be also used, as the organoaluminum compound forpreparing aluminoxane, isoprenylaluminum represented by the followingformula (II):

    (i-C.sub.4 H.sub.9).sub.x Al.sub.y (C.sub.5 H.sub.10).sub.z(II)

wherein x, y and z are each a positive number, and z>2x.

The organoaluminum compounds mentioned above may be used singly or incombination.

Solvents used for preparing aluminoxane include aromatic hydrocarbonssuch as benzene, toluene, xylene, cumene and cymene; aliphatichydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane,hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane,cyclohexane, cyclooctane and methylcyclopentane; petroleum fractionssuch as gasoline, kerosine and gas oil; and halides of theabove-mentioned aromatic, aliphatic and alicyclic hydrocarbons,particularly chlorides and bromides thereof. In addition thereto, etherssuch as ethyl ether and tetrahydrofuran may be also used. Of thesesolvents, particularly preferred are aromatic hydrocarbons.

Examples of the compounds which react with the transition metal compound(A) to form an ion pair (hereinafter sometimes referred to as "component(B-2)"), which are used for the first and the second olefinpolymerization catalysts, include Lewis acid, ionic compounds, boranecompounds and carborane compounds, as described in National Publicationsof International Patent No. 501950/1989 and No. 502036/1989, JapanesePatent Laid-Open Publications No. 179005/1992, No. 179006/1992, No.207703/1992 and No. 207704/1992, and U.S. Pat. No. 547,718.

The Lewis acid includes Mg-containing Lewis acid, Al-containing Lewisacid and B-containing Lewis acid. Of these, B-containing Lewis acid ispreferred.

The Lewis acid containing a boron atom (B-containing Lewis acid) is, forexample, a compound represented by the following formula:

    BR.sup.6 R.sup.7 R.sup.8

wherein R⁶, R⁷ and R⁸ are each independently a phenyl group which mayhave a substituent such as a fluorine atom, a methyl group and atrifluoromethyl group, or a fluorine atom.

Examples of the compounds represented by the above formula includetrifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris (3,5-dimethylphenyl)boron. Of these, tris(pentafluorophenyl)boronis particularly preferred.

The ionic compound used in the invention is a salt comprising a cationiccompound and an anionic compound. An anion reacts with the transitionmetal compound (A) to make the transition metal compound (A) cationicand to form an ion pair so as to stabilize the transition metal cationseed. Examples of such anions include organoboron compound anion andorganoarsenic compound anion, organoaluminum compound anion. Preferredis such anion as is relatively bulky and stabilizes the transition metalcation species. Examples of cations include metallic cation,organometallic cation, carbonium cation, tripium cation, oxonium cation,sulfonium cation, phosphonium cation and ammonium cation. Morespecifically, there can be mentioned triphenylcarbenium cation,tributylammonium cation, N,N-dimethylammonium cation and ferroceniumcation.

Of these, preferred are ionic compounds containing a boron compound asanion. More specifically, examples of trialkyl-substituted ammoniumsalts include triethylammoniumtetra(phenyl)boron,tripropylammoniumtetra(phenyl)boron,tri(n-butyl)ammoniumtetra(phenyl)boron,trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o-tolyl)boron,tributylammoniumtetra(pentafluorophenyl)boron,tripropylammoniumtetra(o,p-dimethylphenyl)boron,tributylammoniumtetra(m,m-dimethylphenyl)boron,tributylammoniumtetra(p-trifluoromethylphenyl)boron,tri(n-butyl)ammoniumtetra(o-tolyl)boron andtri(n-butyl)ammoniumtetra(4-fluorophenyl)boron.

Examples of N,N-dialkylanilinium salts includeN,N-dimethylaniliniumtetra(phenyl)boron,N,N-diethylaniliniumtetra(phenyl)boron andN,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

Examples of dialkylammonium salts includedi(n-propyl)ammoniumtetra(pentafluorophenyl)boron anddicyclohexylammoniumtetra(phenyl)boron.

Examples of triarylphosphonium salts includetriphenylphosphoniumtetra(phenyl)boron,tri(methylphenyl)phosphoniumtetra(phenyl)boron andtri(dimethylphenyl)phosphoniumtetra(phenyl)boron.

Also employable as the ionic compound containing a boron atom aretriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate andferroceniumtetrakis(pentafluorophenyl)borate.

Further, the following compounds can be also employed. (In the ioniccompounds enumerated below, the counter ion is tri(n-butyl)ammonium, butthe counter ion is in no way limited thereto.)

That is, there can be mentioned salts of anion, for example,bis{tri(n-butyl)ammonium}nonaborate,bis{tri(n-butyl)ammonium}decaborate,bis{tri(n-butyl)ammonium}undecaborate,bis{tri(n-butyl)ammonium}dodecaborate,bis{tri(n-butyl)ammonium}decachlorodecaborate,bis{tri(n-butyl)ammonium}dodecachlorododecaborate,tri(n-butyl)ammonium-1-carbadecaborate,tri(n-butyl)ammonium-1-carbaundecaborate,tri(n-butyl)ammonium-1-carbadodecaborate,tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate andtri(n-butyl)ammoniumbromo-1-carbadecaborate.

Moreover, borane compounds and carborane compounds can be also employed.These compounds are employed as the Lewis acid or the ionic compounds.

Examples of the borane compounds and the carborane compounds include:

borane and carborane complex compounds and salts of carborane anion, forexample, decaborane(14), 7,8-dicarbaundecaborane(13),2,7-dicarbaundecaborane(13),undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,dodecahydride-11-methyl-2,7-dicarbaundecaborane,tri(n-butyl)ammonium-6-carbadecaborate(14),tri(n-butyl)ammonium-6-carbadecaborate(12),tri(n-butyl)ammonium-7-carbaundecaborate(13),tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12),tri(n-butyl)ammoniumdodecahydride- 8-methyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbundecaborate,tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborateand tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate;and

carborane and salts of carborane, for example, 4-carbanonaborane(14),1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14),dodecahydride-1-phenyl-1,3-dicarbanonaborane,dodecahydride-1-methyl-1,3-dicarbanonaborane andundecahydride-1,3-dimethyl-1,3-dicarbanonaborane.

Furthermore, the following compounds can be also employed. (In the ioniccompounds enumerated below, the counter ion is tri(n-butyl)ammonium, butthe counter ion in no way limited thereto.)

That is, there can be mentioned salts of metallic carborane and metallicborane anion, for example,tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbononaborate)cobaltate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III),tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),tri(n-butyl)ammoniumbis(dodecahydridedicarbadodecaborate)cobaltate(III),bis{tri(n-butyl)ammonium}bis(dodecahydridedodecaborate)nickelate(III),tris{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)chromate(III),bis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)manganate(IV),bis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)cobaltate(III)andbis{tri(n-butyl)ammonium}bis(undecahydride-7-carbaundecaborate)nickelate(IV).

The compounds (B-2) which react with the transition metal compound (A)to form an ion pair can be used in combination of two or more kinds.

The organoaluminum compound (C) (hereinafter sometimes referred to as"component (C)") used for the second olefin polymerization catalyst ofthe invention is, for example, an organoaluminum compound represented bythe following formula (III):

    R.sup.9.sub.n AlX.sub.3-n                                  (III)

wherein R⁹ is a hydrocarbon group of 1 to 12 carbon atoms, X is ahalogen atom or a hydrogen atom, and n is 1 to 3.

In the above formula (III), R⁹ is a hydrocarbon group of 1 to 12 carbonatoms, e.g., an alkyl group, a cycloalkyl group or an aryl group.Particular examples thereof include methyl, ethyl, n-propyl, isopropyl,isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl andtolyl.

Examples of such organoaluminum compounds (C) include:

trialkylaluminums, such as trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum, trioctylaluminum andtri(2-ethylhexyl)aluminum;

alkenylaluminums, such as isoprenylaluminum,

dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, diisopropylaluminum chloride,diisobutylaluminum chloride and dimethylaluminum bromide;

alkylaluminum sesquihalides, such as methylaluminum sesquichloride,ethylaluminum sesquichloride, isopropylaluminum sesquichloride,butylaluminum sesquichloride and ethylaluminum sesquibromide;

alkylaluminum dihalides, such as methylaluminum dichloride,ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminumdibromide; and

alkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride.

Also employable as the organoaluminum compound (C) is a compoundrepresented by the following formula (IV):

    R.sup.9.sub.n AlL.sub.3-n                                  (IV)

wherein R⁹ is the same hydrocarbon as in the above formula (III); L is--OR¹⁰ group, --OSiR¹¹ ₃ group, --OAlR¹² ₂ group, --NR¹³ ₂ group,--SiR¹⁴ ₃ group or --N(R¹⁵)AlR¹⁶ ₂ group; n is 1 to 2; R¹⁰, R¹¹, R¹² andR¹⁶ are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl orthe like; R¹³ is hydrogen, methyl, ethyl, isopropyl, phenyl,trimethylsilyl or the like; and R¹⁴ and R¹⁵ are each methyl, ethyl orthe like.

Examples of such organoaluminum compounds (C) include:

(1) compounds represented by the formula R⁹ _(n) Al(OR¹⁰)_(3-n') forexample, dimethylaluminum methoxide, diethylaluminum ethoxide anddiisobutylaluminum methoxide;

(2) compounds represented by the formula R⁹ _(n) Al(OSiR¹¹ ₃)_(3-n), forexample, Et₂ Al(OSiMe₃), (iso-Bu)₂ Al(OSiMe₃) and (iso-Bu)₂ Al(OSiEt₃);

(3) compounds represented by the formula R⁹ _(n) Al(OAlR¹² ₂)_(3-n), forexample, Et₂ AlOAlEt₂ and (iso-Bu)₂ AlOAl(iso-Bu)₂ ;

(4) compounds represented by the formula R⁹ _(n) Al(NR¹³ ₂)_(3-n), forexample, Me₂ AlNEt₂, Et₂ AlNHMe, Me₂ AlNHEt, Et₂ AlN(SiMe₃)₂ and(iso-Bu)₂ AlN(SiMe₃)₂ ;

(5) compounds represented by the formula R⁹ _(n) Al(SiR¹⁴ ₃)_(3-n), forexample, (iso-Bu)₂ AlSiMe₃ ; and

(6) compounds represented by the formula R⁹ _(n) Al(N(R¹⁵)AlR¹⁶₂)_(3-n), for example, Et₂ AlN(Me)AlEt₂ and (iso-Bu)₂AlN(Et)Al(iso-Bu)₂.

Of the organoaluminum compounds represented by the formulas (III) and(IV), the compounds represented by the formulas R⁹ ₃ Al, R⁹ _(n)Al(OR¹⁰)_(3-n) and R⁹ _(n) Al(OAlR¹² ₂)_(3-n) are preferred, and thecompounds having these formulas wherein R is an isoalkyl group and n is2 are particularly preferred.

In the present invention, water may be used as a catalyst component inaddition to the component (A) , the component (B-1), the component(B-2)and the component (C). As the water employable in the invention, therecan be mentioned water dissolved in a polymerization solvent describedlater, and adsorbed water or water of crystallization contained in acompound or a salt used for preparing the component (B-1).

The first olefin polymerization catalyst of the invention can beprepared by mixing the component (A) and the component (B-1) (or thecomponent (B-2)), and if desired water (as a catalyst component), in aninert hydrocarbon medium (solvent) or an olefin medium (solvent).

There is no specific limitation on the order of mixing those components,but it is preferred that the component (B-1) (or the component (B-2)) ismixed with water, followed by mixing with the component (A).

The second olefin polymerization catalyst of the invention can beprepared by mixing the component (A), the component (B-1) (or thecomponent (B-2)) and the component (C), and if desired water (as acatalyst component), in an inert hydrocarbon medium (solvent) or anolefin medium (solvent).

There is no specific limitation on the order of mixing those components.However, when the component (B-1) is used, it is preferred that thecomponent (B-1) is mixed with the component (C), followed by mixing withthe component (A). When the component (B-2) is used, it is preferredthat the component (C) is mixed with the component (A), followed bymixing with the component (B-2).

In the mixing of each components, an atomic ratio (Al/transition metal)of aluminum in the component (B-1) to the transition metal in thecomponent (A) is in the range of usually 10 to 10,000, preferably 20 to5,000; and a concentration of the component (A) is in the range of about10⁻⁸ to 10⁻¹ mol/liter-medium, preferably 10⁻⁷ to 5×10⁻²mol/liter-medium.

When the component (B-2) is used, a molar ratio (component (A)/component(B-2)) of the component (A) to the component (B-2) is in the range ofusually 0.01 to 10, preferably 0.1 to 5; and a concentration of thecomponent (A) is in the range of about 10⁻⁸ to 10⁻¹ mol/liter-medium,preferably 10⁻⁷ to 5×10⁻² mol/liter-medium.

In the preparation of the second olefin polymerization catalyst of theinvention, an atomic ratio (Al_(c) /Al_(B-1)) of the aluminum atom(Al_(c)) in the component (C) to the aluminum atom (Al_(B-1)) in thecomponent (B-1) is in the range of usually 0.02 to 20, preferably 0.2 to10.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) is in the range of 0.5 to 50, preferably 1 to 40.

The above-mentioned each components may be mixed in a polymerizer, or amixture of those components beforehand prepared may be fed to apolymerizer.

If the components are beforehand mixed, the mixing temperature is in therange of usually -50° to 150° C., preferably -20° to 120° C.; and thecontact time is in the range of 1 to 1,000 minutes, preferably 5 to 600minutes. The mixing temperature may be varied while the components aremixed and contacted with each other.

Examples of the media (solvents) used for preparing the olefinpolymerization catalyst according to the invent ion include;

aliphatic hydrocarbons, such as propane, butane, pentane, hexane,heptane, octane, decane, dodecane and kerosine;

alicyclic hydrocarbons, such as cyclopentane, cyclohexane andmethylcyclopentane;

aromatic hydrocarbons, such as benzene, toluene and xylene;

halogenated hydrocarbons, such as ethylene chloride, chlorobenzene anddichcloromethane; and

mixtures of these hydrocarbons.

Next, the third and the fourth olefin polymerization catalysts accordingto the invention are described.

The third olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) an compound which reacts with the transition metal compound toform an ion pair;

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier.

The fourth olefin polymerization catalyst according to the inventioncomprises:

a solid catalyst component comprising:

a fine particle carrier,

(A) a transition metal compound represented by the above formula (i),and

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) an compound which reacts with the transition metal compound toform an ion pair,

said transition metal compound (A) and said at least one compound (B)being supported on the fine particle carrier; and

(C) an organoaluminum compound.

The transition metal compound (A) used for the third and the fourtholefin polymerization catalysts of the invention is the same as that forthe aforesaid first and second olefin polymerization catalysts, and isrepresented by the above formula (I).

Examples of the organoaluminum oxy-compounds (B-1) used for the thirdand the fourth olefin polymerization catalysts of the invention are thesame as those used for the first and the second olefin polymerizationcatalysts.

Examples of the compounds (B-2) which react with the transition metalcompound (A) to form an ion pair and used for the third and the fourtholefin polymerization catalysts of the invention are the same as thoseused for the first and the second olefin polymerization catalysts.

Examples of the organoaluminum compounds (C) used for the fourth olefinpolymerization catalyst of the invention are the same as those used forthe second olefin polymerization catalyst.

The fine particle carrier used for the third and the fourth olefinpolymerization catalysts of the invention is an inorganic or organiccompound, and is a particulate or granular solid having a particlediameter of 10 to 300 μm, preferably 20 to 200 μm.

The inorganic carrier is preferably porous oxide, and examples thereofinclude SiO₂, Al₂ O₃, MgO, ZrO₂, TiO₂, B₂ O₃, CaO, ZnO, BaO, ThO₂, andmixtures thereof such as SiO₂ --MgO, SiO₂ --Al₂ O₃, SiO₂ --TiO₂, SiO₂--V₂ O₅, SiO₂ --Cr₂ O₃ and SiO₂ --TiO₂ --MgO. Of these, preferred is acarrier containing SiO₂ and/or Al₂ O₃ as its major component.

The above-mentioned inorganic oxides may contain carbonates, sulfates,nitrates and oxides, such as Na₂ CO₃, K₂ CO₃, CaCO₃, MgCO₃, Na₂ SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₂, Na₂ O, K₂ O and Li₂ O, in asmall amount.

The fine particle carrier is varied in its properties depending on thekind and the process for the preparation thereof, but preferably used inthe invention is a carrier having a specific surface area of 50 to 1,000m² /g, preferably 100 to 700 m² /g, and a pore volume of 0.3 to 2.5 cm³/g. The fine particle carrier is used after calcined at 100° to 1,000°C., preferably 150° to 700° C., if necessary.

Also employable as the fine particle carrier in the invention is agranular or particulate solid of an organic compound having a particlediameter of 10 to 300 μm. Examples of the organic compounds include(co)polymers prepared mainly from α-olefins of 2 to 14 carbon atoms suchas ethylene, propylene, 1-butene and 4-methyl-1-pentene, and(co)polymers prepared mainly from vinylcyclohexane or styrene.

The fine particle carrier may contain a surface hydroxyl group or water.In this case, the surface hydroxyl group is contained in an amount ofnot less than 1.0% by weight, preferably 1.5 to 4.0% by weight, morepreferably 2.0 to 3.5% by weight; and water is contained in an amount ofnot less than 1.0% by weight, preferably 1.2 to 20% by weight, morepreferably 1.4 to 15% by weight. The water contained in the fineparticle carrier means water which is adsorbed on the surface of thefine particle carrier.

The amount (% by weight) of the adsorbed water and the amount (% byweight) of the surface hydroxyl group in the fine particle carrier canbe determined in the following manner.

Amount of Adsorbed Water

The weight reduction of the fine particle carrier after drying at 200°C. under ordinary pressure for 4 hours in a stream of nitrogen ismeasured, and a percentage of the weight after the drying to the weightbefore the drying is calculated.

Amount of Surface Hydroxyl Group

The weight of the fine particle carrier after drying at 200° C. underordinary pressure for 4 hours in a stream of nitrogen is taken as X (g). The carrier is calcined at 1,000° C. for 20 hours to obtain a calcinedproduct containing no surface hydroxyl group. The weight of the calcinedproduct thus obtained is taken as Y (g). The amount (% by weight) of thesurface hydroxyl group is calculated from the following formula.

    Amount (wt. %) of surface hydroxyl group={(X-Y)/X}×100

If a fine particle carrier having a specific amount of adsorbed water ora specific amount of surface hydroxyl group as described above is used,an olefin polymerization catalyst capable of preparing an olefin polymerhaving excellent particle properties and having high polymerizationactivities can be obtained.

Further, in the third and the fourth olefin polymerization catalysts ofthe invention, such water as described in the first and the secondolefin polymerization catalysts may be used as a catalyst component.

The third olefin polymerization catalyst of the invention (i.e., solidcatalyst component) can be prepared by mixing the fine particle carrier,the component (A) and the component (B-1) (or the component (B-2)) , andif desired water (catalyst component), in an inert hydrocarbon medium(solvent) or an olefin medium (solvent) . In the mixing of thosecomponents, the component (C) can be further added.

There is no specific limitation on the order of mixing those components.

However, preferred processes are:

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2), and then with the component(A), followed by mixing with water if desired;

a process in which a mixture of the component (B-1) (or the component(B-2)) and the component (A) is mixed and contacted with the fineparticle carrier, followed by mixing with water if desired; and

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)) and water, followed bymixing with the component (A).

In the mixing of each components, the component (A) is used in an amountof usually 10⁻⁶ to 5×10⁻³ mol, preferably 3×10⁻⁶ to 10⁻³ mol, per 1 g ofthe fine particle carrier; and a concentration of the component (A) isin the range of about 5×10⁻⁶ to 2×10⁻² mol/liter-medium, preferably2×10⁻⁵ to 10⁻² mol/liter-medium. An atomic ratio (Al/transition metal)of aluminum in the component (B-1) to the transition metal in thecomponent (A) is in the range of usually 10 to 3,000, preferably 20 to2,000. When the component (B-2) is used, a molar ratio (component(A)/component (B-2)) of the component (A) to the component (B-2) is inthe range of usually 0.01 to 10, preferably 0.1 to 5.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) is in the range of 0.5 to 50, preferably 1 to 40.

The temperature for mixing the components is in the range of usually-50° to 150° C., preferably -20° to 120° C.; and the contact time is inthe range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The mixingtemperature may be varied while the components are mixed and contactedwith each other.

The fourth olefin polymerization catalyst according to the invention isformed from the above-mentioned third olefin polymerization catalyst(solid catalyst component) and the organoaluminum compound (C) . Thecomponent (C) is used in an amount of not ,more than 500 mol, preferably5 to 200 mol, per 1 g of the transition metal atom in the component (A)contained in the solid catalyst component.

The third and the fourth olefin polymerization catalysts of theinvention may contain other components useful for the olefinpolymerization than the above-described components.

Examples of the inert hydrocarbon media (solvents) used for preparingthe third and the fourth olefin polymerization catalysts of theinvention are the same as those used for the first and the second olefinpolymerization catalysts.

Next, the fifth and the sixth olefin polymerization catalysts accordingto the invention are described.

The fifth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) an compound which reacts with the transition metal compound toform an ion pair; and

a prepolymerized olefin polymer produced by prepolymerization.

The sixth olefin polymerization catalyst according to the inventioncomprises:

a fine particle carrier;

(A) a transition metal compound represented by the above formula (I);

(B) at least one compound selected from a group consisting of

(B-1) an organoaluminum oxy-compound, and

(B-2) an compound which reacts with the transition metal compound toform an ion pair;

(C) an organoaluminum compound; and

a prepolymerized olefin polymer produced by prepolymerization.

Examples of the fine particle carrier used for the fifth and the sixtholefin polymerization catalysts of the invention are the same as thosefor the aforesaid third and fourth olefin polymerization catalysts.

The transition metal compound (A) used for the fifth and the sixtholefin polymerization catalysts of the invention is the same as that forthe aforesaid first and second olefin polymerization catalysts, and isrepresented by the above formula (I) .

Examples of the organoaluminum oxy-compounds (B-1) used for the fifthand the sixth olefin polymerization catalysts of the invention are thesame as those used for the first and the second olefin polymerizationcatalysts.

Examples of the compounds (B-2) which react with the transition metalcompound (A) to form an ion pair and used for the fifth and the sixtholefin polymerization catalysts of the invention are the same as thoseused for the first and the second olefin polymerization catalysts.

Examples of the organoaluminum compounds (C) used for the sixth olefinpolymerization catalyst of the invention are the same as those used forthe second olefin polymerization catalyst.

Further, in the fifth and the sixth olefin polymerization catalysts ofthe invention, such water as described in the first and the secondolefin polymerization catalysts may be used as a catalyst component.

The fifth olefin polymerization catalyst of the invention can beprepared by prepolymerizing a small amount of an olefin to the solidcatalyst component. The solid catalyst component is obtained by mixingthe fine particle carrier, the component (A) and the component (B-1) (orthe component (B-2)), and if desired water, in an inert hydrocarbonmedium (solvent) or an olefin medium (solvent). In the mixing of thosecomponents, the component (C) can be further added.

There is no specific limitation on the order of mixing those components.

However, preferred processes are:

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)), and then with thecomponent (A), followed by mixing with water if desired

a process in which a mixture of the component (B-1) (or the component(B-2)) and the component (A) is mixed and contacted with the fineparticle carrier, followed by mixing with water if desired; and

a process in which the fine particle carrier is mixed and contacted withthe component (B-1) (or the component (B-2)) and water, followed bymixing with the component (A).

The mixing of the components is desirably carried out with stirring.

In the mixing of each components, the component (A) is used in an amountof usually 10⁻⁶ to 5×10⁻³ mol, preferably 3×10⁻⁶ to 10³ mol, per 1 g ofthe fine particle carrier; and a concentration of the component (A) isin the range of about 5×10⁻⁶ to 2×10⁻² mol/liter-medium, preferably 10⁻⁵to 10⁻² mol/liter-medium. An atomic ratio (Al/transition metal) ofaluminum in the component (B-1) to the transition metal in the component(A) is in the range of usually 10 to 3,000, preferably 20 to 2,000. Whenthe component (B-2) is used, a molar ratio (component (A)/component(B-2)) of the component (A) to the component (B-2) is in the range ofusually 0.01 to 10, preferably 0.1 to 5.

When water is used as a catalyst component, a molar ratio (Al_(B-1) /H₂O) of the aluminum atom (Al_(B-1)) in the component (B-1) to water (H₂O) ) is in the range of 0.5 to 50, preferably 1 to 40.

The temperature for mixing the components is in the range of usually-50° to 150° C., preferably -20° to 120° C.; and the contact time is inthe range of 1 to 1,000 minutes, preferably 5 to 600 minutes. The mixingtemperature may be varied while the components are mixed and contactedwith each other.

The fifth olefin polymerization catalyst of the invention can beprepared by prepolymerizing an olefin in the presence of theabove-mentioned components. The prepolymerization can be carried out byintroducing an olefin into an inert hydrocarbon medium (solvent) in thepresence of the components and if necessary the component (C).

In the prepolymerization, the component (A) is used in an amount ofusually 10⁻⁵ to 2×10⁻² mol/liter, preferably 5×10⁻⁵ to 10⁻² mol/liter.The prepolymerization temperature is in the range of -20° to 80° C.,preferably 0° to 50° C.; and the prepolymerization time is 0.5 to 100hours, preferably about 1 to 50 hours.

The olefin used for the prepolymerization is selected from olefins whichare used for polymerization, and it is preferable to use the samemonomer as used in the polymerization or a mixture of the same monomeras used in the polymerization and an α-olefin.

In the olefin polymerization catalyst of the invention obtained asabove, it is desired that the transition metal atom is supported in anamount of about 10⁻⁶ to 10⁻³ g·atom, preferably 2×10⁻⁶ to 3×10⁻⁴ g·atom,per 1 g of the fine particle carrier; and the aluminum atom is supportedin an amount of about 10⁻³ to 10⁻¹ g·atom, preferably 2×10⁻³ to 5×10⁻²g·atom, per 1 g of the fine particle carrier. Further, it is alsodesired that the component (B-2) is supported in an amount of 5×10⁻⁷ to0.1 g·atom, preferably 2×10⁻⁷ to 3×10⁻² g·atom, in terms of the boronatom contained in the component (B-2).

The amount of the prepolymerized polymer prepared by theprepolymerization is desired to be in the range of about 0.1 to 500 g,preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g ofthe fine particle carrier.

The sixth olefin polymerization catalyst of the invention is formed fromthe above-mentioned fifth olefin polymerization catalyst (component) andthe organoaluminum compound (C) . The organoaluminum compound (C) isused in an amount of not more than 500 mol, preferably 5 to 200 mol, per1 g·atom of the transition metal atom in the component (A).

The fifth and the sixth olefin polymerization catalysts of the inventionmay contain other components useful for the olefin polymerization thanthe above-described components.

Examples of the inert hydrocarbon solvents used for the fifth and thesixth olefin polymerization catalysts of the invention are the same asthose used for preparing the aforesaid first and second olefinpolymerization catalysts.

Polyolefins obtained by the use of the olefin polymerization catalystsas described above have a narrow molecular weight distribution, a narrowcomposition distribution and a high molecular weight and the olefinpolymerization catalysts have a high polymerization activity.

Further, when olefins of 3 or more carbon atoms are polymerized in thepresence of the olefin polymerization catalysts, polyolefins havingexcellent stereoregularity can be obtained.

Next, the process for olefin polymerization according to the presentinvention is described.

An olefin is polymerized in the presence of any of the above-describedolefin polymerization catalysts. The polymerization may be carried outby a liquid phase polymerization process such as a suspensionpolymerization or by a gas phase polymerization.

In the liquid phase polymerization process, the same inert hydrocarbonsolvent as used in the preparation of the catalyst can be used, or theolefin itself can be also used as a solvent.

In the polymerization of an olefin using the first or the secondpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g.atom/liter, preferably 10⁻⁷ to 10⁻⁴ g.atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system.

In the polymerization of an olefin using the third or the fourthpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g.atom/liter, preferably 10⁻⁷ to 10⁻⁴ g.atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system. In this case, an aluminoxane which isnot supported on the carrier may be employed, if desired.

In the polymerization of an olefin using the fifth or the sixthpolymerization catalyst, the catalyst is used in an amount of usually10⁻⁸ to 10⁻³ g.atom/liter, preferably 10⁻⁷ to 10⁻⁴ g.atom/liter, interms of a concentration of the transition metal atom of the component(A) in the polymerization system. In this case, an aluminoxane which isnot supported on the carrier may be employed, if desired.

In the slurry polymerization, the temperature for the olefinpolymerization is in the range of usually -50° to 100° C. preferably 0°to 90° C. In the liquid phase polymerization, the temperature is in therange of usually 0° to 250° C., preferably 20° to 200° C. In the gasphase polymerization process, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The polymerization pressure isin the range of usually atmospheric pressure to 100 kg/cm², preferablyatmospheric pressure to 50 kg/cm². The polymerization reaction can becarried out either batchwise, semicontinuously or continuously. Further,the polymerization may be performed in two or more stages havingdifferent reaction conditions.

The molecular weight of the resulting olefin polymer can be regulated byallowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature.

Examples of the olefins to be polymerized using the olefinpolymerization catalysts of the invention include:

α-olefins of 2 to 20 carbon atoms, such as ethylene, propylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; and

cycloolefins of 3 to 20 carbon atoms, such as cyclopentene,cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5, 8, 8a-octahydronaphthalene.

Also employable are styrene, vinylcyclohexane, diene, etc.

When the olefin polymerization catalyst of the invention is used topolymerize an α-olefin of 3 or more carbon atoms, obtainable is apolymer having a lower melting point as compared with a polymer obtainedby using a conventional metallocene type catalyst, even though thepolymers have the almost the same molecular weight. Further, when thecatalyst of the invention is used, a copolymer having a low meltingpoint can be obtained even if the amount of recurring units derived froma comonomer is small.

If an α-olefin of 3 or more carbon atoms is polymerized using the olefinpolymerization catalyst of the invention, a great number of inverselyinserted monomer units are present in the molecules of the resultantolefin polymer. It is known that in the α-olefin prepared by apolymerization of an α-olefin of 3 or more carbon atoms in the presenceof a chiral metallocene catalyst, 2,1-insertion or 1,3-insertion takesplace in addition to the ordinary 1,2-insertion, whereby an inverselyinserted unit such as a 2,1-insertion or 1,3-insertion is formed in theolefin polymer molecule (see: Makromol. Chem., Rapid Commun., 8,305(1987), by K. Soga, T. Shiono, S. Takemura and W. Kaminsky). It is alsoknown that when inverse insertions are present in the olefin polymermolecule, the melting point of the olefin polymer becomes low for itsstereoregularity (see: Polymer, 30, 1350 (1989) , by T. Tsutsui, N.Ishimura, A. Mizuno, A. Toyota and N. Kashiwa).

In the molecule of the olefin polymer obtained by polymerizing anα-olefin of 3 or more carbon atoms using the olefin polymerizationcatalyst of the invention, a great number of inversely inserted monomerunits are present, and hence it is presumed that the melting point ofthe olefin polymer is lower than the melting point of an olefin polymerhaving almost the same molecular weight which is obtained by the use ofa conventional catalyst.

The propylene polymer, the propylene copolymer and the propyleneelastomer according to the invention are described hereinafter.

Propylene Polymer

The propylene polymer of the invention is a polymer comprising propyleneunits, but it may contain constituent units derived from other olefinsthan propylene in an amount of less than 0.5% by mol, preferably lessthan 0.3% by mol, more preferably less than 0.1% by mol.

The propylene polymer of the invention has a triad tacticity of not lessthan 90% preferably not less than 93%, more preferably not less than95%. The term "triad tacticity" means a proportion of such chains ofthree propylene units (i.e., chains consisting of three propylene unitscontinuously bonded) that the directions of methyl branches in thepropylene chain are the same as each other and each propylene units arebonded to each other with head-to-tail bonds, to total three propyleneunits-chains in the polymer, and this term is sometimes referred to as"mm fraction" hereinafter.

The triad tacticity can be determined from a ¹³ C-NMR spectrum of thepropylene polymer.

The ¹³ C-NMR spectrum is measured in the following manner. A sample of50 to 60 mg is completely dissolved in a mixed solvent containing about0.5 ml of hexachlorobutadiene, o-dichlorobenzene or1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene (i.e.,lock solvent) in a NMR sample tube (diameter: 5 mm), and then subjectedto a proton perfect decoupling method at 120° C. to measure the ¹³ C-NMRspectrum. The measurement is conducted under the conditions of a flipangle of 45° and a pulse interval of not less than 3.4 T₁ (T₁ is amaximum value with respect to a spin-lattice relaxation time of themethyl group). T₁ of the methylene group and T₁ of the methine group areeach shorter than that of the methyl group, and hence the magnetizationrecovery of all carbons under these conditions is not less than 99%.

With respect to the chemical shift, the methyl group of the third unitin the 5 propylene units-chain consisting of head-to-tail bonds andhaving the same directions of the methyl branches is set to 21.593 ppm,and the chemical shift of other carbon peak is determined by using theabove-mentioned value as a reference. Accordingly, a peak based on themethyl group of the second unit in the three propylene units-chainhaving PPP(mm) structure appears in the range of 21.1 to 21.8 ppm; apeak based on the methyl group of the second unit in the three propyleneunits-chain having PPP(mr) structure appears in the range of 20.2 to21.1 ppm; and a peak based on the methyl group of the second unit in thethree propylene units-chain having PPP(rr) structure appears in therange of 19.4 to 20.2 ppm.

PPP(mm), PPP(mr) and PPP(rr) have the following 3 propylene units-chainstructure with head-to-tail bonds, respectively. ##STR8##

In addition to the ordered structures represented by the above-describedPPP (mm), PPP (mr) and PPP (rr) , the propylene polymer has a structure(i) containing an inversely inserted unit based on the 2,1-insertion anda structure (ii) containing an inversely inserted unit based on the1,3-insertion, in small amounts. ##STR9##

The aforementioned definition of the mm fraction is not applied to thepropylene units having the carbons attached with marks A, B, C and Damong the carbons attached with marks A to Fo The carbon A and thecarbon B resonate in the region of 16.5 to 17.5 ppm, the carbon Cresonates in the vicinity of 20.8 ppm (mr region), and the carbon Dresonates in the vicinity of 20.7 ppm (mr region). In the structure (i)and the structure (ii), however, not only the peak of the methyl groupbut also the peaks of the adjacent methylene and methine groups must beconfirmed.

In the structure (ii), --(CH₂)₃ -- unit is produced and a unitcorresponding to one methyl group disappears as a result of hydrogentransfer polymerization.

Accordingly, the mm fraction in all of the polymer chains can berepresented by the following formula: ##EQU1## wherein ΣICH₃ denotes thetotal areas of all peaks derived from the methyl groups.

Further, I.sub.αδ and I₆₂ γ are an area of αδ peak (resonance in thevicinity of 37.1 ppm) and an area of βγ peak (resonance in the vicinity27.3 ppm), respectively. Naming of these methylene peaks was made inaccordance with a method by Carman, et al. (Rubber Chem. Tachnol., 44(1971), 781).

In the polymerization to prepare a propylene polymer, the 1,2-insertionof the propylene monomer mainly takes place, but the 2,1-insertion orthe 1,3-insertion thereof sometimes takes place. The 2,1-insertion formsthe inversely inserted unit represented by the aforementioned structure(i) in the polymer chain. The proportion of the 2,1-propylene monomerinsertions to the all propylene insertions was calculated by thefollowing formula. ##EQU2##

Likewise, the proportion of the 1,3-propylene monomer insertionsrepresented by the aforementioned structure (ii) to the all propyleneinsertions was calculated by the following formula. ##EQU3##

In the propylene polymer according to the invention, the proportion ofthe inversely inserted units based on the 2,1-insertion in all propyleneinsertions, as measured by ¹³ C-NMR, is not less than 0.7%, preferably0.7 to 2.0%. Further, in the propylene polymer of the invention, theproportion of the inversely inserted units based on the 1,3-insertion inall propylene insertions is not more than 0.05%, preferably not morethan 0.04%, more preferably not more than 0.03%.

The propylene polymer of the invention has an intrinsic viscosity η!, asmeasured in decahydronaphthalene at 135° C., of 0.1 to 12 dl/g,preferably 0.5 to 12 dl/g, more preferably 1 to 12 dl/g.

The propylene polymer of the invention can be prepared by polymerizingpropylene in the presence of, for example, the aforesaid olefinpolymerization catalysts. The polymerization can be carried out by aliquid phase polymerization (e.g., a suspension polymerization and asolution polymerization) or a gas phase polymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, or propylenecan be also used as a solvent.

In the suspension polymerization, the temperature for polymerizingpropylene is in the range of usually -50° to 100° C., preferably 0° to90° C. In the solution polymerization, the temperature is in the rangeof usually 0° to 250° C., preferably 20° to 200° C. In the gas phasepolymerization, the temperature is in the range of usually 0° to 120°C., preferably 20° to 100° C. The polymerization pressure is in therange of usually atmospheric pressure to 100 kg/cm², preferablyatmospheric pressure to 50 kg/cm². The polymerization reaction can becarried out either batchwise, semicontinuously or continuously. Further,the polymerization can be carried out in two or more stages havingdifferent reaction conditions.

The molecular weight of the resultant propylene polymer can be regulatedby allowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature and the polymerization pressure.

Propylene Copolymer

The propylene copolymer of the invention is a propylene/ethylene randomcopolymer containing propylene units in an amount of 95 to 99.5% by mol,preferably 95 to 99% by mol, more preferably 95 to 98% by mol, andcontaining ethylene units in an amount of 0.5 to 5% by mol, preferably 1to 5% by mol, more preferably 2 to 5% by mol.

Such propylene copolymer may contain constituent units derived fromother olefins than propylene and ethylene in an amount of not more than5% by mol.

In the propylene copolymer of the invention, the triad tacticity of thepropylene unit chain consisting of head-to-tail bonds, as measured by ¹³C-NMR, is not less than 90%, preferably not less than 93%, morepreferably not less than 96%.

The triad tacticity (mm fraction) of the propylene copolymer can bedetermined from a ¹³ C-NMR spectrum of the propylene copolymer and thefollowing formula: ##EQU4## wherein PPP (mm); PPP (mr) and PPP (rr)denote peak areas derived from the methyl groups of the second units inthe following three propylene units-chains consisting of head-to-tailbonds, respectively: ##STR10##

The ¹³ C-NMR spectrum of the propylene copolymer can be measured in thesame manner as described for the propylene polymer. The spectrumrelating to the methyl carbon region (16-23 ppm) can be classified intothe first region (21.1-21.9 ppm), the second region (20.3-21.0 ppm), thethird region (19.5-20.3 ppm) and the fourth region (16.5-17.5 ppm). Eachpeak in the spectrum was assigned with reference to a literature"Polymer", 30 (1989) 1350.

In the first region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (mm) resonates.

In the second region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (mr) resonates and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm).

In the third region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (rr) resonates and the methylgroup (EPE-methyl group) of a propylene unit whose adjacent units areethylene units resonate (in the vicinity of 19.8 ppm).

Further, the propylene copolymer has the following structures (i) and(iii) containing an inversely inserted unit. ##STR11##

Of the carbons attached with marks A to G, a peak of the carbon C and apeak of the carbon C' appear in the second region, a peak of the carbonG appears in the third region, and a peak of the carbon A and a peak ofthe carbon B appear in the fourth region.

Of the peaks which appear in the first to fourth regions as describedabove, peaks which are not based on the three propylene units-chainconsisting of head-to-tail bonds are peaks based on the PPE-methylgroup, the EPE-methyl group, the carbon C, the carbon C', the carbon G,the carbon A and the carbon B.

The peak area based on the PPE-methyl group can be evaluated by the peakarea of the PPE-methine group (resonance in the vicinity of 30.6 ppm),and the peak area based on the EPE-methyl group can be evaluated by thepeak area of the EPE-methine group (resonance in the vicinity of 32.9ppm). The peak area based on the carbon C can be evaluated by 1/2 asmuch as the sum of the peak areas of the carbon F and the carbon E bothhaving the inversely inserted structure (structure (i) ) (resonance inthe vicinity of 35.6 ppm and resonance in the vicinity of 35.4 ppm,respectively). The peak area based on the carbon C' can be evaluated by1/2 as much as the sum of the peak areas of the αβ methylene carbonshaving the inversely inserted structure (structure (iii)) (resonance inthe vicinity of 34.3 ppm and resonance in the vicinity of 34.5 ppm,respectively). The peak area based on the carbon G can be evaluated bythe peak area of the adjacent methine carbon (resonance in the vicinityof 33.7 ppm).

Accordingly, by subtracting these peak areas from the total peak areasof the second region and the third region, the peak areas based on thethree propylene units-chains (PPP (mr) and PPP (rr)) consisting ofhead-to-tail bonds can be obtained.

Since the positions of the carbon A peak and the carbon B peak have noconcern with the peak of the three propylene units-chain (PPP), they donot need to be taken into account. 10 Thus, the peak areas of PPP (mm),PPP(mr) and PPP (rr) can be evaluated, and hence the triad tacticity ofthe propylene unit chain consisting of head-to tail bonds can bedetermined.

In the propylene copolymer of the invention, the 5 proportion of theinversely inserted units based on the 2,1-insertion in all propyleneinsertions, as measured by ¹³ C-NMR, is not less than 0.5%, preferably0.5 to 1.5%. Further, in the propylene copolymer of the invention, theproportion of the inversely inserted units based on the 1,3-insertion ofthe propylene monomer in all propylene insertions is not more than0.05%, preferably not more than 0.04%, more preferably not more than0.03%.

In the polymerization, the 1,2-insertion of the propylene monomer (i.e.,the methylene side is bonded to the catalyst) mainly takes place, butthe 2,1-insertion thereof sometimes takes place. The 2,1-insertion formsthe inversely inserted unit in the polymer.

The proportion of the 2,1-insertions to the all propylene insertions inthe propylene copolymer was calculated by the following formula withreference to "Polymer", 30 (1989) 1350. ##EQU5##

Naming of the peaks in the above formula was made in accordance with amethod by Carman, et al. (Rubber Chem. Tachnol., 44 (1971), 781).I.sub.αδ denotes a peak area of the αδ peak.

The proportion (%) of the amount of the three propylene units-chainsbased on the 1,3-insertion was determined by dividing 1/2 as much as thearea of the βγ peak (resonance in the vicinity of 27.4 ppm) by the sumof all the methyl group peaks and 1/2 as much as the βγ peak, and thenmultiplying the resulting value by 100.

The propylene copolymer of the invention has an intrinsic viscosity η!,as measured in decahydronaphthalene at 135° C., of 0.1 to 12 dl/g,preferably 0.5 to 12 dl/g, more preferably 1 to 12 dl/g.

The propylene copolymer of the invention can be prepared bycopolymerizing propylene and ethylene in the presence of, for example,the aforesaid olefin polymerization catalysts. The copolymerization canbe carried out by a liquid phase polymerization (e.g., a suspensionpolymerization and a solution polymerization) or a gas phasepolymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, and propyleneand/or ethylene can be also used as a solvent.

In the suspension polymerization, the temperature for copolymerizingpropylene and ethylene is in the range of usually -50° to 100° C.,preferably 0° to 90° C. In the solution polymerization, the temperatureis in the range of usually 0° to 250° C., preferably 20° to 200° C. Inthe gas phase polymerization, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The copolymerization pressureis in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The copolymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the copolymerization can be carried out in two ormore stages having different reaction conditions.

The molecular weight of the resultant propylene copolymer can beregulated by allowing hydrogen to exist in the copolymerization systemor by varying the copolymerization temperature and the copolymerizationpressure.

Propylene Elastomer

The propylene elastomer of the invention is a propylene/ethylene randomcopolymer containing propylene units in an amount of 50 to 95% by mol,preferably 60 to 93% by mol, more preferably 70 to 90% by mol, andcontaining ethylene units in an amount of 5 to 50% by mol, preferably 7to 40% by mol, more preferably 10 to 30% by mol.

Such propylene elastomer may contain constituent units derived fromother olefins than propylene and ethylene in an amount of not more than10% by mol.

In the propylene elastomer of the invention, the triad tacticity of thepropylene unit chain consisting of head-to-tail bonds, as measured by ¹³C-NMR, is not less than 90.0%, preferably not less than 92.0%, morepreferably not less than 95.0%.

The triad tacticity (mm fraction) of the propylene elastomer can bedetermined from a ¹³ C-NMR spectrum of the propylene elastomer and thefollowing formula: ##EQU6## wherein PPP (mm), PPP (mr) and PPP (rr) havethe same meanings as defined before.

The ¹³ C-NMR spectrum of the propylene elastomer can be measured in thesame manner as described for the propylene polymer. The spectrumrelating to the methyl carbon region (19-23 ppm) can be classified intothe first region (21.2-21.9 ppm), the second region (20.3-21.0 ppm) andthe third region (19.5-20.3 ppm). Each peak in the spectrum was assignedwith reference to a literature "Polymer", 30 (1989) 1350.

In the first region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (mm) resonates.

In the second region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (mr) resonates and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm).

In the third region, the methyl group of the second unit in the threepropylene units-chain represented by PPP (rr) resonates and the methylgroup (EPE-methyl group) of a propylene unit whose adjacent units areethylene units resonates (in the vicinity of 19.8 ppm).

Further, the propylene elastomer has the following structures (iii) and(iv) containing an inversely inserted unit. ##STR12##

Of the carbons attached with marks C and G, a peak of the carbon C' anda peak of the carbon C" appear in the second region, and a peak of thecarbon G and a peak of the carbon G' appear in the third region.

Of the peaks which appear in the first to third regions as describedabove, peaks which are not based on the 3 propylene units-chainconsisting of head-to-tail bonds are peaks based on the PPE-methylgroup, the EPE-methyl group, the carbon C', the carbon C", the carbon Gand the carbon G'.

The peak area based on the PPE-methyl group can be evaluated by the peakarea of the PPE-methine group (resonance in the vicinity of 30.6 ppm),and the peak area based on the EPE-methyl group can be evaluated by thepeak area of the EPE-methine group (resonance in the vicinity of 32.9ppm). The peak area based on the carbon C' can be evaluated by twice asmuch as the peak area of the methine carbon (resonance in the vicinityof 33.6 ppm) to which the methyl group of the carbon G is directlybonded; and the peak area based on the carbon C" can be evaluated by thepeak area of the adjacent methine carbon (resonance in the vicinity of33.2 ppm) of the methyl group of the carbon G'. The peak area based onthe carbon G can be evaluated by the peak area of the adjacent methinecarbon (resonance in the vicinity of 33.6 ppm); and the peak area basedon the carbon G' can be also evaluated by the adjacent methine carbon(resonance in the vicinity of 33.2 ppm).

Accordingly, by subtracting these peak areas from the total peak areasof the second region and the third region, the peak areas based on the 3propylene units-chains (PPP(mr) and PPP(rr)) consisting of head-to-tailbonds can be obtained.

Thus, the peak areas of PPP(mm), PPP(mr) and PPP(rr) can be evaluated,and hence the triad tacticity of the propylene unit chain consisting ofhead-to tail bonds can be determined.

In the propylene elastomer of the invention, the proportion of theinversely inserted units based on the 2,1-insertion in all propyleneinsertions, as measured by ¹³ C-NMR, is not less than 0.5%, preferably0.5 to 2.0%, more preferably 0.5 to 1.5%. Further, in the propyleneelastomer of the invention, the proportion of the inversely insertedunits based on the 1,3-insertion is not more than 0.05%, preferably notmore than 0.03%.

The proportion of the 2,1-insertions to all of the propylene insertionsin the propylene elastomer was calculated by the following formula withreference to "Polymer", 30 (1989) 1350. ##EQU7##

Naming of the peaks in the above formula was made in accordance with amethod by Carman, et al. (Rubber Chem. Tachnol., 44 (1971), 781),I.sub.αδ denotes a peak area of the αδ peak.

If it is difficult to determine the peak area of I.sub.αδ or the likedirectly from the spectrum because of overlapping of the peaks, a carbonpeak having the corresponding area can be substituted therefor.

The proportion (%) of the amount of the three propylene units-chainsbased on the 1,3-insertion was determined by dividing 1/2 as much as thearea of the βγ peak (resonance in the vicinity of 27.4 ppm) by the sumof all the methyl group peaks and 1/2 as much as the βγ peak, and thenmultiplying the resulting value by 100.

The propylene elastomer of the invention has an intrinsic viscosity η!,as measured in decahydronaphthalene at 135° C., of 0.1 to 12 dl/g,preferably 0.5 to 12 dl/g, more preferably 1 to 12 dl/g.

The propylene elastomer of the invention can be prepared bycopolymerizing propylene and ethylene in the presence of, for example,the aforesaid olefin polymerization catalysts. The copolymerization canbe carried out by a liquid phase polymerization (e.g., a suspensionpolymerization and a solution polymerization) or a gas phasepolymerization.

In the liquid phase polymerization, the same inert hydrocarbon solventas used for preparing the aforesaid catalyst can be used, and propyleneand/or ethylene can be also used as a solvent.

In the suspension polymerization, the temperature for copolymerizingpropylene and ethylene is in the range of usually -50° to 100° C.,preferably 0° to 90° C. In the solution polymerization, the temperatureis in the range of usually 0° to 250° C., preferably 20° to 200° C. Inthe gas phase polymerization, the temperature is in the range of usually0° to 120° C., preferably 20° to 100° C. The copolymerization pressureis in the range of usually atmospheric pressure to 100 kg/cm²,preferably atmospheric pressure to 50 kg/cm². The copolymerizationreaction can be carried out either batchwise, semicontinuously orcontinuously. Further, the copolymerization can be carried out in two ormore stages having different reaction conditions.

The molecular weight of the resultant propylene elastomer can beregulated by allowing hydrogen to exist in the copolymerization systemor by varying the copolymerization temperature and the copolymerizationpressure.

EFFECT OF THE INVENTION

The novel transition metal compound according to the invention can beused as an olefin polymerization catalyst component.

The olefin polymerization catalyst of the invention has highpolymerization activity and polyolefins prepared by the use of thecatalyst have a narrow molecular weight distribution and a narrowcomposition distribution. When an α-olefin of 3 or more carbon atoms isused, obtainable is a polymer having a lower melting point as comparedwith a polymer obtained by using a conventional metallocene catalysteven though the polymers have almost the same molecular weight.

By the use of the catalyst of the invention, a copolymer having a lowmelting point can be obtained even if the amount of recurring unitsderived from a comonomer is small. Further, because of a small amount ofa solvent-soluble components, the resultant copolymer is excellent invarious properties such as transparency, heat-sealing properties andanti-blocking properties. Moreover, the synthesis of polypropylene canbe made with fewer reaction steps and is more economical, as comparedwith the synthesis using a conventional metallocene catalyst whenpolypropylene having almost the same molecular weight is produced.

When a copolymer elastomer mainly containing ethylene units andpropylene units is prepared using the olefin polymerization catalyst ofthe invention, the resultant elastomer has a high molecular weight. Suchcopolymer elastomer has a high strength, and hence when used as amodifier, the elastomer exhibits excellent effects in the improvement ofimpact strength and hardness of polyolefins. When the copolymerelastomer is used to prepare a propylene block copolymer, the resultantcopolymer is well-balanced between heat resistance, rigidity ortransparency and impact strength because the molecular weight of thecopolymer elastomer can be increased. Also in the preparation ofpolyethylene, the resultant polyethylene is excellent in mechanicalstrength such as impact strength, tensile strength and flexural strengthfor the same reason.

The propylene polymer of the invention is excellent in rigidity, heatresistance, surface hardness, glossiness, transparency and impactresistance. Hence, it can be suitably used for various industrial parts,containers, films, nonwoven fabrics, stretched yarns, etc.

The propylene copolymer of the invention is excellent in transparency,rigidity, surface hardness, heat resistance, heat-sealing properties,anti-blocking properties, bleed resistance and impact resistance. Hence,it can be suitably used for films, sheets, containers, stretched yarns,nonwoven fabrics, etc.

The propylene elastomer of the invention is excellent in heatresistance, impact absorbing properties, transparency, heat-sealingproperties and anti-blocking properties. Hence, it can be singly usedfor films, sheets, etc., and moreover it can be suitably used as amodifier of a thermoplastic resin.

EXAMPLE

The present invention is described in more detail with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

In the present invention, an intrinsic viscosity η!, a molecular weightdistribution (Mw/Mn), a stereoregularity (mmmm), a proportion ofinversely inserted units and a melting point (Tm) are measured by thefollowing methods.

Further, in some examples, a melt flow rate (MFR), a flexural modulus(FR), a heat distortion temperature (HDT), a heat seal-startingtemperature and a heat seal-starting temperature after heat treatment,an izod impact strength (IZ) and a film impact strength are measured bythe following method.

Intrinsic Viscosity η!

The intrinsic viscosity η! was measured in decahydronaphthalene at 135°C., and expressed by dl/g.

Molecular Weight Distribution (Mw/Mn)

The molecular weight distribution (Mw/Mn) was measured in the followingmanner using GPC-150C produced by Milipore Co.

A separation column of TSK-GNH-HT having a diameter of 72 mm and alength of 600 mm was used, and the column temperature was set to 140° C.A sample (concentration 0.1% by weight, amount: 500 microliters) wasmoved in the column at a rate of 1.0 ml/min using o-dichlorobenzene(available from Wako Junyaku Kogyo K. K.) as a mobile phase and 0.025%by weight of BHT (Takeda Chemical Industries, Ltd.) as an antioxidant. Adifferential refractometer was used as a detector. With respect tostandard polystyrenes, polystyrenes available from Toso Co., Ltd. wereused for Mw <1,000 and Mw>4×10⁶, and polystyrenes available fromPressure Chemical Co. were used for 1,000<Mw<4×10⁶.

Stereoregularity (mm Triad Tacticity and mmmm Pentad Tacticity)

mm triad tacticity was measured as mentioned above.

mmmm pentad tacticity was measured as follows.

About 50 mg of a sample was completely dissolved in a mixed solventcontaining 0.5 ml of o-dichlorobenzene (or hexachlorobutadiene) and 0.1ml of deuterated benzene in a NMR sample tube (diameter: 5 mm) at about120° C., and then a ¹³ C-NMR spectrum was measured (nuclear species: ¹³C, mode: perfect proton decoupling, temperature: 120° C.) by a GX500type NMR measuring apparatus produced by Japan Electron OpticsLaboratory Co., Ltd.

On the ¹³ C-NMR spectrum, an area of a peak having resonance in thelowest magnetic field (21.8 ppm according to A. Zambelli, P. Locateill,G. Bajo and F. A. Bovey, "Macromolecules", 8, 687 (1975)) was divided bya total area of all peaks of the methyl groups, and the resultant valuewas taken as a mmmm pentad tacticity value.

Proportion of Inversely Inserted Units

For each of the polymers obtained in Examples 3 and 4 and ComparativeExample 1, the proportions of the inversely inserted units based on the2,1-insertion and the 1,3-insertion of a propylene monomer present inthe propylene chain of the polymer were determined from the ¹³ C-NMRspectrum and the following formulas. ##EQU8## wherein Iαα is the totalarea of the αα carbon peaks (resonances in the vicinity of 42.0 ppm and46.2 ppm), Iαβ is the total area of the αβ carbon peaks (resonances inthe vicinity of 30.2 ppm and 35.6 ppm), and Iαδ is an area of the αδcarbon peak (resonance in the vicinity of 37.1 ppm). Naming of the peaks(e.g., αα) was made in accordance with the classification by Carman, etal. (C. J. Carman and C. E. Wilkes, Rubber Chem. Technol., 44, 781(1971)).

The proportions of the inversely inserted units in other examples weremeasured by the method described before.

Melting Point (Tm)

The melting point was determined from an endothermic curve given byheating about 5 mg of a sample charged in an aluminum pan to 200° C. ata rate of 10° C./min, keeping it at 200° C. for 5 minutes, then coolingit to room temperature at a rate of 20° C./min and heating it again at arate of 10° C./min. The measurement was conducted using a DSC-7 typeapparatus produced by Perkin Elmer Co.

Melt Flow Rate (MFR)

The MFR is measured in accordance with ASTM D 1238 under a load of 2.16kg at 230° C.

Flexural Modulus

The FM is measured in accordance with ASTM D 790 using a specimen of12.7 mm (width)×6.4 mm (thickness)×127 mm (length) prepared by injectionmolding at a resin temperature of 200° C. and a molding temperature of40° C. at a distance between spuns of 100 mm and a rate of flexing of 2mm/min.

Heat Distortion Temperature (HDT)

The HDT is measured in accordance with ASTM D 648 under a load of 4.6kg/cm².

Heat Seal-starting Temperature and Heat Seal-starting Temperature afterHeat Treatment

with respect to a T-die film having a width of 30 cm and a thickness of50 μm prepared using a single screw extruder having a diameter of 30 mmunder the conditions of a resin temperature of 210° C. (at a portion ofdicer of extruder), a take-off speed of 3 m/min and a temperature ofcooling roll of 25° C., heat seal of two films is carried out using aheat sealer by sealing at various seal for temperatures under theconditions of a heat seal pressure of 2 kg/cm², a seal time of 1 secondand a width of 5 mm, to prepare a sealed film. The above-prepared sealedfilm was allowed to cool.

The heat seal-staring temperature is defined as a temperature of theheat sealer when the peeling resistance of the sealed film becomes 300g/25 mm, under such conditions that the sealed film is peeled off at 23°C., a peeling speed of 200 mm/min and a peeling angle of 180°.

Separately, another sealed film was subjected to heat treatment at 50°C. for 7 days. The heat seal-starting temperature after heat treatmentwas measured using the heat treated specimen.

Izod Impact Strength (IZ)

The IZ is measured in accordance with ASTM D 256 at 23° C. using anotched specimen of 12.7 mm (width)×6.4 mm (thickness)×64 mm (length).

The specimen is prepared by injection molding at a resin temperature of200° C. and a molding temperature of 40° C. using a polypropylenecomposition obtained by dry-blending 20% by weight of a polymeraccording to the present invention and 80% by weight of a polypropylene(HIPOL¹⁹⁸, grade J 700, melt flow rate: 11 g/10 min (at 230° C.),density: 0.91, manufactured by Mitsui petrochemical Industries, Ltd. ),and melt-kneading at 200° C. using a twin-screw extruder.

Film Impact Strength

The film impact strength is measured using a film impact tester(manufactured by Toyo Seiki K. K., diameter of impact head bulb: 1/2inch(12.7 mm φ)).

EXAMPLE 1 Synthesis ofrac-dimethylsilyl-bis{1-(4-isopropyl-2,7-dimethylindenyl) }zirconiumdichloride Synthesis of 4-isopropyl-2,7-dimethylindene (Compound 1)

A 1-liter reactor thoroughly purged with nitrogen was charged with 90 g(0.67 mol) of aluminum chloride and 150 ml of carbon disulfide, and tothe reactor was dropwise added a solution of 47 ml (0.30 mol) ofp-cymene and 33 ml (0.3 mol) of methacryloyl chloride in 30 ml of carbondisulfide at a temperature of 20° to 25° C. The mixture was reacted atroom temperature for 12 hours and then added to 1 kg of ice, followed byextraction with ether. The obtained ether solution was washed withsaturated aqueous solution of sodium hydrogencarbonate and then water,and concentrated to obtain 68 g of an oil. This oil was purified bymeans of silica gel column chromatography (eluting solution: n-hexane)to obtain 42 g of a mixture (mixture 1) of2,4-dimethyl-7-propyl-1-indanone and 2,7-dimethyl-4-isopropyl-1-indanone(yield: 67%).

A 1-liter reactor thoroughly purged with nitrogen was charged with 2.82g (0.075 mol) of lithium aluminum hydride and 200 ml of ether, and tothe reactor was dropwise added a mixture of 36.5 g (0.18 mol) of themixture 1 and 150 ml of ether while cooling with ice. After the dropwiseaddition was completed, the mixture was stirred at room temperature for30 minutes and then refluxed for 1 hour. After the reaction wascompleted, the reaction mixture was worked up by conventional procedureand then extracted with ether. The obtained ether solution was washedwith saturated aqueous solution of sodium hydrogencarbonater and water,and dried over sodium sulfate. The ether layer was concentrated toobtain 36 g of a solid. This solid was slurried in 100 ml of n-hexaneand the solvent was evaporated off to obtain 30 g of a mixture (mixtureNo. 2) of 2,4-dimethyl-7-isopropyl-1-indanol and2,7-dimethyl-4-isopropyl-1-indanol (yield: 82%).

A 1-liter reactor thoroughly purged with nitrogen was charged with 25 g(0.12 mol) of the mixture 2 and 500 ml of benzene. To the reactor wasadded 50 mg (0.55 mmol) of paratoluene sulfonic acid monohydrate, andthe mixture was refluxed for 1 hour. After the reaction was completed,the reaction mixture was poured into 30 ml of saturated sodiumhydrogencarbonate solution. The resulting organic layer was washed withwater and then dried over anhydrous sodium sulfate. The organic layerwas concentrated to give an oil which was then distilled to obtain 20 gof the title compound 1 (yield: 90%).

The NMR data of the title compound 1 is shown in Table 1.

Synthesis of 1,1'-dimethylsilyl-bis (4-isopropyl-2,7-dimethylindene)(Compound 2)

A 200-ml reactor thoroughly purged with nitrogen was charged with 9.5 g(51 mmol) of the title compound 1, 7.7 ml (51 mmol) oftetramethylethylenediamine and 60 ml of diethyl ether, followed bycooling to -10° C. To the solution was added a solution ofn-butyllithium (51 mmol) in hexane. After heating to room temperature,the solution was cooled again to -10° C., 3.1 ml (25.5 mol) ofdimethyldichlorosilane was dropwise added over 30 minutes and thereaction was carried out for 1 hour. After the reaction was completed,the reaction solution was added to 40 ml of saturated aqueous solutionof ammonium chloride, then extracted with n-hexane, washed with waterand dried over magnesium sulfate. The salt was removed, and theresulting organic layer was concentrated under a reduced pressure toobtain an yellow oil which was purified by means of silica gel columnchromatography (eluting solution: n-hexane) to obtain 5.4 g of the titlecompound 2 as a colorless amorphous product (yield: 50%).

The NMR data of the title compound 2 is shown in Table 1.

Synthesis of rac-dimethylsilyl-bis{1-(4-isopropyl-2,7-dimethyindenyl)}zirconium dichloride (Compound 3)

A 300-ml reactor thoroughly purged with nitrogen was charged with 5.4 g(12.6 mmol) of the title compound 2 and 100 ml of tetrahydrofuran, andthe content in the reactor was cooled to -78° C. and stirred. To thereactor was dropwise added 16 ml of n-butyllithium (a solution inn-hexane, 1.58N, 25.2 mmol) over 20 minutes, and the mixture was stirredfor another 1 hour with keeping the temperature to prepare an anionsolution which was then slowly heated to room temperature.

Separately, 100 ml of tetrahydrofuran was charged in a 300-ml reactorthoroughly purged with nitrogen, cooled to -78° C. and stirred. To thereactor was slowly added 2.94 g (12.6 mmol) of zirconium tetrachloride,followed by heating to room temperature. To the mixture was dropwiseadded the anion solution prepared above over 30 minutes, followed bystirring at room temperature for 12 hours. After the reaction wascompleted, the reaction mixture was concentrated under a reducedpressure and a solid precipitated was washed three times with 300 ml ofhexane to remove insoluble substances. The obtained hexane solution wasconcentrated to about 50 ml, and the solution was cooled at 6° C. for 12hours. ¹ H-NMR analysis of the solid obtained, 1.78 g (yield: 24%),showed that it was a mixture of a racemic modification and a mesoisomer(4:1). This mixture was recrystallized from 100 ml of hexane to obtain0.22 g of the title compound 3 as an yellow prismatic crystal (yield:3%). The result of the FD mass spectrometry of the title compound 3 was588 (M⁺).

The NMR data of the title compound 3 is shown in Table 1.

EXAMPLE 2 Synthesis ofrac-diphenylsilyl-bis{1-(4-isopropyl-2,7-dimethylindenyl) }zirconiumdichloride Synthesis of1,1'-diphenylsily-bis-(4-isopropyl-2,7-dimethylidene) (Compound 4)

The procedure of the synthesis of the title compound 2 in Example 1 wasrepeated except that 120 mg of copper cyanide was used in place oftetramethylethylenediamine and 5.7 ml of diphenyldichlorosilane in placeof dimethyldichlorosilane.

The title compound 4 was obtained as a colorless amorphous product in anamount of 7.2 g (yield: 49%).

The NMR data of the title compound 4 is shown in Table 1.

Synthesis of rac-diphenylsily-bis{1-(4-isopropyl-2,7-dimethylidene)}zirconium dichloride (Compound 5)

The procedure of the synthesis of the title compound 3 in Example 1 wasrepeated except that 7.1 g (12.9 mmol) of the title compound 4 was usedin place of the title compound 2 and 3,01 of zirconium tetrachloride inplace of 2.94 g.

The title compound 5 was obtained as an yellow prismatic crystal in anamount of 1.10 g (yield: 12%). The result of the FD mass spectrometry ofthe compound 5 was 712 (M⁺).

The NMR data of the title compound 5 is shown in Table 1.

                  TABLE 1    ______________________________________    NMR Data    Compound    No.      .sup.1 H-NMR Spectrum (CDCl.sub.3, ppm)    ______________________________________    1        1.26(6H, d, J=7.2Hz), 2.70(3H, s),             2.38(3H, s), 2.88(1H, q, J=7.0Hz), 3.27(2H, s),             6.54(1H, s), 6.90(1H, s), 7.10(1H, s)    2        1.60(12H, d, J=7.2Hz), 0.94˜1.14(6H, m),             1.91˜2.06(6H, m), 2.26(6H, s), 2.71(2H, q,             J=7.2Hz), 3.49(2H, s), 6.49(2H, s), 6.74(2H, s),             7.06(2H, s)    3        1.20(12H, d, J=7.2Hz), 1.29(6H, s), 2.21(6H, s),             2.33(6H, s), 2.81(2H, q, J=7.0Hz), 6.70(2H, s),             7.01(2H, s), 7.26(2H, s)    4        1,06(6H, d, J=7.2Hz), 1.26(6H, d, J=7.2Hz),             1.80(3H, s), 2.10(6H, s), 2.24(3H, s), 2.80(2H,             s), 4.36(4H, br.s), 6.16(2H, s), 6.60-7.68(14H, m)    5        0.92(12H, d, J=6.8Hz), 2.02(6H, s), 2.36(6H, s),             2.60(2H, q, J=6.8Hz), 6.80(2H, s), 6.90(2H, s),             6.99(2H, s), 7.45-7.50(6H, m), 8.12-8.16(4H, m)    ______________________________________

EXAMPLE 3

A 2-liter autoclave thoroughly purged with nitrogen was charged with 500g of propylene, followed by warming to 40° C. To the autoclave wereadded 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane and0.001 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopropyl-1-indenyl)}zirconiumdichloride to polymerize propylene at 50° C. for 1 hour. After thepolymerization, the autoclave was released to remove propylene, and theresulting polymer was dried at 80° C. for 10 hours.

The amount of the polymer obtained was 158 g and the polymerizationactivity was 158 kg-PP/mmol-Zr. The polymer had an η! of 4.55 dl/g, aMw/Mn of 2.2, an mmmm pentad value of 95.5%, a proportion of the2,1-insertion of 0.90% and a Tm of 147° C.

EXAMPLE 4

A 2-liter autoclave thoroughly purged with nitrogen was charged with 500g of propylene, followed by warming to 40° C. To the autoclave wereadded 0.2 mmol of triethylaluminum, 0.001 mmol (in terms of Zr atom) ofrac-diphenylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride and 0.002 mmol (in terms of B atom) oftris(pentafluorophenyl)boron to polymerize propylene at 50° C. for 1hour. After the polymerization, the autoclave was released to removepropylene, and the resulting polymer was dried at 80° C. for 10 hours.

The amount of the polymer obtained was 94 g and the polymerizationactivity was 94 kg-PP/mmol-Zr. The polymer had an η! of 4.75 dl/g, aMw/Mn of 2.3, an mmmm pentad value of 96.4%, a proportion of the2,1-insertion of 0.80% and a Tm of 148° C.

COMPARATIVE EXAMPLE 1

A 2-liter autoclave thoroughly purged with nitrogen was charged with 500g of propylene, followed by warming to 40° C. To the autoclave wereadded 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane and0.001 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-methyl-4-isopropylindenyl)}zirconiumdichloride to polymerize propylene at 50° C. for 1 hour. After thepolymerization, the autoclave was released to remove propylene, and theresulting polymer was dried at 80° C. for 10 hours.

The amount of the polymer obtained was 125 g and the polymerizationactivity was 125 kg-PP/mmol-Zr. The polymer had an η! of 3.47 dl/g, aMw/Mn of 2.1, an mmmm pentad value of 96.2%, a proportion of the2,1-insertion of 0.40% and a Tm of 152° C.

EXAMPLE 5

A 1-liter glass reactor thoroughly purged with nitrogen was charged with500 ml of toluene, and propylene was fed at a rate of 100 liters/hr,followed by warming to 50° C. To the reactor was added a solutionobtained by precontacting 3.5 mmol of methylaluminoxane and 0.01 mmol(in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopylindenyl)}zirconiumdichloride in toluene, to polymerize propylene at 50° C. for 20 minutes.After the polymerization, the solution was poured in amethanolhydrochloric acid solution, and the resulting mixture wasfiltered to give a polymer which was dried at 80° C. for 10 hours.

The amount of the polymer obtained was 32.6 g and the polymerizationactivity was 8.2 kg-PP/mmol-Zr. The polymer had an η! of 1.37 dl/g, aMw/Mn of 2.2 and a Tm of 148° C.

COMPARATIVE EXAMPLE 2

The procedures of Example 5 were repeated except thatrac-ethylenebis{1-(2,4,7-trimethylindenyl)}zirconium dichloride was usedin place ofrac-dimethylsilyl-bis{(1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride.

The amount of the polymer obtained was 23.1 g and the polymerizationactivity was 5.8 kg-PP/mmol-Zr. The polymer had an η! of 0.44 dl/g, aMw/Mn of 2.3 and a Tm of 150° C. This polymer had a molecular weightextremely lower than that of the polymer obtained in Example 5.

EXAMPLE 6 Preparation of Solid Catalyst Component (a)

A 500-ml reactor thoroughly purged with nitrogen was charged with 25 gof silica (F-948, available from Fuji Devison Co.) having been dried at200° C. for 6 hours in a stream of nitrogen and 310 ml of toluene, andthe system was set to 0° C. with stirring. To the system was dropwiseadded 90 ml of an organoaluminum oxy-compound (methylaluminoxaneavailable from Schering Co., diluted in toluene, 2.1 mol/liter) over 60minutes in a nitrogen atmosphere. Then, the mixture was reacted at thesame temperature for 30 minutes and further at 90° C. for 4 hours. Thereaction system was allowed to cool and when the temperature was reachedto 60° C., the supernatant was decantated off and the residue was washedthree times with 150 ml of toluene at room temperature to obtain a solidcatalyst component (a) containing 6.8 mmol of Al per 1 g of silica.

Preparation of Solid Catalyst Component (b)

A 200-ml reactor thoroughly purged with nitrogen was charged with 50 mlof n-hexane, and to the reactor were added 10.5 mmol (in terms of Alatom) of the solid catalyst component (a) obtained above and 0.03 mmol(in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl) }zirconiumdichloride, followed by stirring for 20 minutes. Then, 100 ml ofn-hexane and 0.9 mmol of triisobutylaluminum were successively added tothe reactor and the mixture was stirred for 10 minutes. Thereafter, apropylene gas (2.2 liters/hr) was passed through the reactor at 20° C.for 4 hours to prepolymerize propylene. The supernatant was decantatedoff and then the residue washed three times with 150 ml of toluene toobtain a solid catalyst component (b) in which Zr and Al were supportedin amounts of 0.011 mmol and 4.48 mmol, respectively, per 1 g of thesolid catalyst.

Polymerization

750 ml of purified n-hexane was introduced into a 2-liter autoclavethoroughly purged with nitrogen, and stirred at 25° C. for 20 minutes ina propylene/ethylene mixed gas atmosphere (ethylene: 3.6% by mol). Tothe reaction system were added 1.0 mmol of triisobutylaluminum and 0.002mmol (in terms of Zr atom) of the solid catalyst component (b), and thetemperature of the system was elevated to 50° C. to polymerize themonomers for 1 hour at a total pressure of 2 kg/cm² -G. After thepolymerization, the reaction mixture was filtered to remove the solvent,the resulting polymer was washed with hexane and dried at 80° C. for 10hours.

The amount of the polymer (powder) obtained was 75 g, the amount (SP) ofthe polymer dissolved in the solvent was 1.9 g (2.5% by weight), and thepolymerization activity was 38.5 kg-copolymer/mmol-Zr. The polymerpowder had an MFR of 6.0 dg/min, a Mw/Mn of 2.6, an ethylene content of2.9% by mol and a Tm of 126° C.

EXAMPLE 7 Preparation of Solid Catalyst Components (c)

A 200-ml reactor thoroughly purged with nitrogen was charged with 50 mlof n-hexane, and to the reactor were added 10.5 mmol (in terms of Alatom) of the solid catalyst component (a) obtained above and 0.03 mmol(in terms of Zr atom) of rac-diphenylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl) }zirconium dichloride, followed bystirring for 20 minutes. Then, 100 ml of n-hexane and 0.9 mmol oftriisobutylaluminum were successively added to the reactor, and themixture was stirred for 10 minutes. Thereafter, propylene gas (2.2liters/hr) was passed through the reactor at 20° C. for 4 hours topolymerize propylene. The supernatant was decantated off, and then theresidue was washed three times with 150 ml of toluene to obtain a solidcatalyst component (c) in which Zr and Al were supported in amounts of0.011 mmol and 4.55 mmol, respectively, per 1 g of the solid catalyst.

Polymerization

750 ml of purified n-hexane was introduced into a 2-liter autoclavethoroughly purged with nitrogen, and stirred at 25° C. for 20 minutes ina propylene/ethylene mixed gas atmosphere (ethylene: 3.6% by mol). Tothe reaction system were added 1.0 mmol of triisobutylaluminum and 0.002mmol (in terms of Zr atom) of the solid catalyst component (c) , and thetemperature of the system was elevated to 50° C. to polymerize themonomers for 1 hour at a total pressure of 2 kg/cm² -G. After thepolymerization, the reaction mixture was filtered to remove the solvent,the resulting polymer was washed with hexane and dried at 80° C. for 10hours.

The amount of the polymer (powder) obtained was 59 g, the amount (SP) ofthe polymer dissolved in the solvent was 2.5 g (4.0% by weight), and thepolymerization activity was 30.7 kg-copolymer/mmol-Zr. The polymerpowder had an MFR of 5.8 dg/min, a Mw/Mn of 2.6, an ethylene content of2.9% by mol and a Tm of 127° C.

COMPARATIVE EXAMPLE 3 Preparation of Solid Catalyst Component (d)

A 200-ml reactor thoroughly purged with nitrogen was charged with 50 mlof n-hexane, and to the reactor were added 10.5 mmol (in terms of Alatom) of the solid catalyst component (a) obtained above and 0.03 mmol(in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2-methyl-4-isopropylindenyl) }zirconiumdichloride, followed by stirring for 20 minutes. Then, 100 ml ofn-hexane and 0.09 mmol of triisobutylaluminum were successively added tothe reactor, and the mixture was stirred for 10 minutes. Thereafter, apropylene gas (2.2 liters/hr) was passed through the reactor at 20° C.for 4 hours to prepolymerize propylene. The supernatant was decantatedoff, and then the residue was washed three times with 150 ml of tolueneto obtain a solid catalyst component (d) in which Zr and Al weresupported in amounts of 0.011 mmol and 4.35 mmol, respectively, per 1 gof the solid catalyst.

Polymerization

750 ml of purified n-hexane was introduced into a 2-liter autoclavethoroughly purged with nitrogen, and stirred at 25° C. for 20 minutes ina propylene/ethylene mixed gas atmosphere (ethylene: 5.2% by mol). Tothe reaction system were added 1.0 mmol of triisobutylaluminum and 0.002mmol (in terms of Zr atom) of the solid catalyst component (d), and thetemperature of the system was elevated to 50° C. to polymerize themonomers for 1 hour at a total pressure of 2 kg/cm² -G. After thepolymerization, the reaction mixture was filtered to remove the solvent,the resulting polymer was washed with hexane and dried at 80° C. for 10hours.

The amount of polymer (powder) obtained was 67 g, and a small amount ofthe polymer adhered to the autoclave wall was observed. The amount (SP)of the polymer dissolved in the solvent was 9.0 g (12.0% by weight). Thepolymerization activity was 38 kg-copolymer/mmol-Zr. The polymer powderhad an MFR of 12 dg/min, a Mw/Mn of 2.5, an ethylene content of 5.0% bymol and a Tm of 127° C.

When the above polymerization procedure is performed in an industrialscale, it is presumed that the polymer adhered to the autoclave wallcauses a reduced heat transfer efficiency, and the high SP value causesnot only a reduced polymer yield but also an increased viscosity of thesolvent removed, resulting in difficult operation.

EXAMPLE 8

A 2-liter autoclave thoroughly purged with nitrogen was charged with 500g of propylene. The temperature of the autoclave was elevated to 40° C.,and to the autoclave were added 0.2 mmol of triisobutylaluminum, 0.2mmol of methylamuminoxane and 0.001 mmol (in terms of Zr atom) ofrac-diphenylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl) }zirconiumdichloride, to polymerize propylene at 50° C. for 1 hour. After thepolymerization, the autoclave was released to remove propylene, and theresulting polymer was dried at 80° C. for 10 hours under a reducedpressure.

The amount of the propylene polymer obtained was 158 g, and thepolymerization activity was 158 kg-polymer/mmol-Zr. The polymer had anintrinsic viscosity η! of 4.55 dl/g. In the propylene polymer, the triadtacticity of the propylene unit chain consisting of head-to-tail bondswas 95.4%, the proportion of the inversely inserted units based on the2,1-insertion of the propylene monomer was 0.87%, and the proportion ofthe inversely inserted units based on the 1,3-insertion of the propylenemonomer was not more than 0.03%.

The polymer had a melt flow rate (MFR) of 12.5 g/10 min, a flexuralmodulus (FM) of 12500 kg/cm², and a heat distortion temperature of 105°C..

EXAMPLE 9

750 ml of hexane was introduced into a 2-liter autoclave thoroughlypurged with nitrogen and stirred at 25° C. for 20 minutes in apropylene/ethylene mixed gas atmosphere (ethylene: 2.9% by mol). To thereaction system were added 0.25 mmol of triisobutylaluminum, 0.5 mmol ofmethylaluminoxane and 0.0015 mmol (in terms of Zr atom) ofrac-diphenylsilyl-bis{1-(2, 7-dimethyl-4-isopropylindenyl) }zirconiumdichloride, and the temperature of the system was elevated to 50° C. topolymerize the monomers for 1 hour while keeping the total pressure at 2kg/cm² -G. After the polymerization, the autoclave was released, theresulting polymer was recovered in a large amount of methanol and driedat 80° C. for 10 hours under a reduced pressure.

The amount of the propylene copolymer obtained was 26.9 g, and thepolymerization activity was 17.9 kg-polymer/mmol-Zr. The copolymer hadan intrinsic viscosity η! of 2.2 dl/g and an ethylene content of 3.0% bymol. In the propylene copolymer, the triad tacticity of of the propyleneunit chain consisting of head-to-tail bonds was 97.3%, the proportion ofthe inversely inserted units based on the 2,1-insertion of the propylenemonomer was 0.9%, and the proportion of the inversely inserted unitsbased on the 1,3-insertion of the propylene monomer was 0.04%.

The film of the copolymer had heat self-starting temperature of 118° C.and a heat seal-starting temperature after heat treatment of 120° C..

The results are shown in Table 2.

EXAMPLE 10

900 ml of hexane was introduced into a 2-liter autoclave thoroughlypurged with nitrogen, and 1 mmol of triisobutylaluminum was addedthereto. After elevating the temperature of the reaction system to 70°C., ethylene was fed to the system to a pressure of 1.5 kg/cm², andpropylene was then fed to a total pressure of 8 kg/cm² -G. Then, to thereaction system were added 0.3 mmol of methylaluminoxane and 0.001 mmol(in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride to polymerize monomers for 20 minutes while propylene wascontinuously fed to keep the total pressure at 8 kg/cm² -G. After thepolymerization, the autoclave was released, the resulting polymer wasrecovered in a large amount of methanol and dried at 110° C. for 10hours under a reduced pressure.

The amount of the propylene copolymer obtained was 21.2 g, and thepolymerization activity was 21 kg-polymer/mmol-Zr. The copolymer had anintrinsic viscosity η! of 1.5 dl/g and an ethylene content of 4.7% bymol. In the propylene copolymer, the triad tacticity of the propyleneunit chain consisting of head-to-tail bonds was 96.9%, the proportion ofthe inversely inserted units based on the 2,1-insertion of the propylenemonomer was 1.1 and the proportion of the inversely inserted units basedon the 1,3-insertion of the propylene monomer was not more than 0.04%.

The film of the copolymer had a heat seal-starting temperature of 107°C. and a heat seal-starting temperature after heat treatment of 111° C..

The results are shown in Table 2.

EXAMPLE 11

900 ml of hexane was introduced into a 2-liter autoclave thoroughlypurged with nitrogen. Then, to the autoclave was added 1 mmol oftriisobutylaluminum and was fed 60 liters of propylene gas. Afterelevating the temperature of the reaction system to 70° C., ethylene wasfed to the system to a total pressure of 8 kg/cm² -G. Then, to thereaction system were added 0.45 mmol of methylaluminoxane and 0.0015mmol (in terms of Zr atom) ofrac-diphenylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride to polymerize the monomers for 40 minutes while ethylene wascontinuously fed to keep the total pressure at 8 kg/cm² -G. After thepolymerization, the autoclave was released, the resulting polymer wasrecovered in a large amount of methanol, and dried at 110° C. for 10hours under a reduced pressure.

The amount of the polymer obtained was 47.2 g. The polymerizationactivity was 31.5 kg-polymer/mmol-Zr. The polymer had an intrinsicviscosity η! of 2.0 dl/g and an ethylene content of 27.0% by mol. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 95.4%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0.88%, andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.05%.

The film of the copolymer had a film impact strength of 6000 kgf.cm/cm,and the composition with polypropylene had IZ of 35 kg.cm/cm and a meltflow rate (MFR) of 9.3 g/10 min.

The results are shown in Table 2.

EXAMPLE 12

900 ml of hexane was introduced into a 2-liter autoclave thoroughlypurged with nitrogen, and 1 mmol of triisobutylaluminum was addedthereto. After elevating the temperature of the reaction system to 70°C., ethylene was fed to the system to a pressure of 2.0 kg/cm², and thenpropylene was fed to the system to a total pressure of 8 kg/cm² -G.Then, to the reaction system were added 0.3 mmol of methylaluminoxaneand 0.001 mmol (in terms of Zr atom) ofrac-dimethylsilyl-bis{1-(2,7-dimethyl-4-isopropylindenyl)}zirconiumdichloride, to polymerize the monomers for 10 minutes while propylenewas continuously fed to keep the total pressure at 8 kg/cm² -G. Afterthe polymerization, the autoclave was released, the resulting polymerwas recovered in a large amount of methanol and dried at 110° C. for 10hours under a reduced pressure.

The amount of the polymer obtained was 16.8 g and the polymerizationactivity was 16.8 kg-polymer/mmol-Zr. The polymer had an intrinsicviscosity η! of 1.7 dl/g and an ethylene content of 8.5% by mol. In thepolymer, the triad tacticity of the propylene unit chain consisting ofhead-to-tail bonds was 95.6%, the proportion of the inversely insertedunits based on the 2,1-insertion of the propylene monomer was 0 62% andthe proportion of the inversely inserted units based on the1,3-insertion of the propylene monomer was not more than 0.05%.

The film of the copolymer had a heat seal-starting temperature of 90° C.and a heat seal-starting temperature after heat treatment of 93° C..

The results are shown in Table 2.

                  TABLE 2    ______________________________________                                       Heat                                       seal-                                Heat   starting          In-             Ethyl-                                seal-  tempera-                                              Film          trnsic  Melt-   ene   starting                                       ture   impact          vis-    ing     content                                tempera-                                       after  strength    Exam- cosity  point   (mol  ture   heat   (kg · cm/    ple    η! (°C.)                          %)    (°C.)                                       treatment                                              cm)    ______________________________________    Ex. 9 2.2     120     3     118    120    --    Ex. 10          1.5     110     4.7   107    111    --    Ex. 11          2       --      27    --     --     6000    Ex. 12          1.7      90     8.5    90     93    --    ______________________________________              IZ of              composition with                           MFR of composition              polypropylene                           with polypropylene    Example   (kgf · cm/cm)                           (g/10 min)    ______________________________________    Ex. 9     --           --    Ex. 10    --           --    Ex. 11    35           9.3    Ex. 12    --           --    ______________________________________

What is claimed is:
 1. A propylene polymer having such propertiesthat:(a) a triad tacticity of three propylene units-chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is 90.0% to 98.0%; (b) aproportion of inversely inserted units based on the 2,1-insertion of apropylene monomer is all propylene insertions, as measured by ¹³ C-NMR,is 0.7 to 2.0%, and a proportion of inversely inserted units based on1,3-insertion of a propylene monomer, as measured by ¹³ C-NMR, is notmore than 0.05%; and (c) an intrinsic viscosity, as measured indecanhydro-naphthalene at 135° C., is in the range of 1.0 to 12 dl/g. 2.A propylene copolymer having such properties that:(a) said copolymercontains propylene units in an amount of 95 to 99.5% by mol and ethyleneunits in an amount of 0.5 to 5% by mol; (b) a triad tacticity of threepropylene units-chain consisting of head-to-tail bonds, as measured by¹³ C-NMR, is 90.0% to 97.3%; (c) a proportion of inversely insertedunits based on the 2,1-insertion of a propylene monomer in all propyleneinsertions, as measured by ¹³ C-NMR, is 0.5 to 1.5%, and a proportion ofinversely inserted units based on the 1,3-insertion of a propylenemonomer, as measured by ¹³ C-NMR, is not more than 0.05%; and (d) anintrinsic viscosity, as measured in decahydronaphthalene at 135° C., isin the range of 1.0 to 12 dl/g.
 3. A propylene elastomer having suchproperties that:(a) said elastomer contains propylene units in an amountof 50 to 95% by mol and ethylene units in an mount of 5 to 50% by mol;(b) a trial tacticity of three propylene units-chain consisting ofhead-to-tail bonds, as measured by ¹³ C-NMR, is 90.0% to 97.3%; (c) aproportion of inversely inserted units based on the 2,1-insertion of apropylene monomer in all propylene insertions, as measured by ¹³ C-NMR,is 0.5 to 2.0%, and a proportion of inversely inserted units based onthe 1,3-insertion of a propylene monomer, as measured by ¹³ C-NMR, isnot more than 0.05%; and (d) an intrinsic viscosity, as measured indecahydronaphthalene at 135° C., is in the range of 1.0 to 12 dl/g.
 4. Apropylene polymer according to claim 1 wherein the 2,1-insertion is 0.7to 1.1%.
 5. A propylene polymer according to claim 2, wherein the2,1-insertion is 0.5 to 1.1%.
 6. A propylene polymer according to claim3, wherein the 2,1-insertion is 0.5 to 1.1%.